Personal care compositions comprising polymers derived from vinyl alcohol ethers and applications thereof

ABSTRACT

The invention provides a personal care composition comprising polymers having the structure:wherein Q, R1, a, b, and c are described herein. The invention further provides hair care compositions comprising the polymers. Particularly, the hair care composition is a hair styling composition that provides hairstyle retention at a relative humidity exceeding about 40 percent. The invention furthermore provides a method of providing hairstyle retention to hair at a relative humidity exceeding about 40 percent, the method comprising applying to hair the hair care composition as described herein.

BACKGROUND Field of the Invention

The invention provides personal care compositions comprising polymersderived from vinyl alcohol ethers. The invention further provides haircare compositions, such as hair styling gels comprising the polymersderived from vinyl alcohol ethers. The invention furthermore provides amethod of providing hairstyle retention at high relative humidity usinghair care compositions comprising polymers derived from vinyl alcoholethers.

Description of Related Art

U.S. Pat. No. 6,533,964 teaches a polymeric compound comprisingpolyvinyl alcohol units characterized in that some or all of thehydroxyl groups on the polyvinyl alcohol units are substituted withoxyalkylene-containing groups to an average molar substitution of atleast 0.3 wherein some or all of the hydroxyl groups on the molecule arecapped with monovalent substituents. The patent further teaches binderresins composed of the polymeric compounds.

U.S. Pat. No. 7,088,572 teaches an electrical double-layer capacitorcomprising an electrolyte. The electrolyte is a polymer gel comprising amatrix polymer. The matrix polymer is a polymeric material having ainterpenetrating or a semi-interpenetrating network structure comprisinga polyvinyl alcohol derivative in combination with a crosslinkablefunctional group-bearing compound.

U.S. Pat. No. 5,112,886 teaches an aqueous dispersion comprising aquaternary nitrogen modified polymer which comprises a polyvinyl alcoholbase chain having a number average molecular weight of 2,000-1,000,000having pendant quaternary nitrogen groups. The patent teaches allantoinsalts of quaternary nitrogen containing polymers for use in skinconditioning, cosmetic and pharmaceutical formulations.

U.S. Pat. No. 5,473,059 teaches a paper, explosive, oil field chemical,agricultural chemical, textile fiber, or personal care product whichincludes cationic water soluble quaternary ammonium ethers ofpolysaccharides or polyols. Examples of polyols include polyvinylalcohol, polyethylene glycol and glycerol.

GB patent 364,323 teaches manufacture of hydroxy-alkyl-polyvinylcompounds by causing an alkylene oxide to act upon a polyvinyl alcohol.Due to their solubility in water, the products are suitable for variousindustrial purposes such as sizing agents for producing plastic massesand the like.

A book titled ‘Polyvinyl Alcohol-Developments’, edited by C. A. Finchand published in 1992 (second edition, Wiley), provides information onsynthesis, industrial production methods, and the physical, chemical andspectroscopic properties of polyvinyl alcohol polymers, includingpolyvinyl butyrals, functional polymers, and ethylene-vinyl alcoholcopolymers.

We have now found that polymers derived from vinyl alcohol ethers haveunique physical, chemical, and mechanical properties. As a result,compositions comprising these polymers have applications in variousindustrial arts, particularly in personal care, and more particularly inhair care.

SUMMARY

In a first aspect, the invention provides a personal care compositioncomprising a polymer having the structure:

wherein each Q is a hydrocarbyl moiety comprising at least one hydroxyland optionally at least one ether; each R₁ is a functionalized orunfunctionalized alkyl; a is a value ranging from about 0.1 to 100percent by weight of the polymer; and each b and c is an independentlyselected value ranging from 0 to about 99.9 percent by weight of thepolymer, with the proviso that the sum of a, b and c for the polymerequals 100 weight percent. Particular, yet non-limiting examples ofpersonal care compositions include hair care compositions, conditioningcompositions, skin care compositions, oral care compositions, face carecompositions, lip care compositions, eye care compositions, after-suncompositions, body care compositions, nail care compositions, anti-agingcompositions, insect repellants, deodorant compositions, color cosmeticcompositions, color-protection compositions, self-tanning compositions,and foot care compositions. More particularly, the personal carecomposition is a hair care composition.

In a second aspect, the invention provides a method of providinghairstyle retention to hair at a relative humidity exceeding about 40%,the method comprising applying onto the hair a hair care compositioncomprising a polymer having the structure:

wherein each Q is a hydrocarbyl moiety comprising at least one hydroxyland optionally at least one ether; each R₁ is a functionalized orunfunctionalized alkyl; a is a value ranging from about 0.1 to 100percent by weight of the polymer; and each b and c is an independentlyselected value ranging from 0 to about 99.9 percent by weight of thepolymer, with the proviso that the sum of a, b and c for the polymerequals 100 weight percent.

DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the hair characteristics test results of hair carecompositions according to the invention in a comparative study.

FIG. 2 depicts the high humidity curl retention test results of haircare compositions according to the invention in a comparative study.

DETAILED DESCRIPTION

Before explaining at least one aspect of the disclosed and/or claimedinventive concept(s) in detail, it is to be understood that thedisclosed and/or claimed inventive concept(s) is not limited in itsapplication to the details of construction and the arrangement of thecomponents or steps or methodologies set forth in the followingdescription or illustrated in the drawings. The disclosed and/or claimedinventive concept(s) is capable of other aspects or of being practicedor carried out in various ways. Also, it is to be understood that thephraseology and terminology employed herein is for the purpose ofdescription and should not be regarded as limiting.

Unless otherwise defined herein, technical terms used in connection withthe disclosed and/or claimed inventive concept(s) shall have themeanings that are commonly understood by those of ordinary skill in theart. Further, unless otherwise required by context, singular terms shallinclude pluralities and plural terms shall include the singular.

All patents, published patent applications, and non-patent publicationsreferenced in any portion of this application are herein expresslyincorporated by reference in their entirety to the same extent as ifeach individual patent or publication was specifically and individuallyindicated to be incorporated by reference.

All of the articles and/or methods disclosed herein can be made andexecuted without undue experimentation in light of the presentdisclosure. While the articles and methods of the disclosed and/orclaimed inventive concept(s) have been described in terms of particularaspects, it will be apparent to those of ordinary skill in the art thatvariations may be applied to the articles and/or methods and in thesteps or in the sequence of steps of the method described herein withoutdeparting from the concept, spirit and scope of the disclosed and/orclaimed inventive concept(s). All such similar substitutes andmodifications apparent to those skilled in the art are deemed to bewithin the spirit, scope and concept of the disclosed and/or claimedinventive concept(s).

As utilized in accordance with the disclosure, the following terms,unless otherwise indicated, shall be understood to have the followingmeanings.

The use of the word “a” or “an” when used in conjunction with the term“comprising” may mean “one,” but it is also consistent with the meaningof “one or more,” “at least one,” and “one or more than one.” The use ofthe term “or” is used to mean “and/or” unless explicitly indicated torefer to alternatives only if the alternatives are mutually exclusive,although the disclosure supports a definition that refers to onlyalternatives and “and/or.”

Throughout this application, the term “about” is used to indicate that avalue includes the inherent variation of error for the quantifyingdevice, the method being employed to determine the value, or thevariation that exists among the study subjects. For example, but not byway of limitation, when the term “about” is utilized, the designatedvalue may vary by plus or minus twelve percent, or eleven percent, orten percent, or nine percent, or eight percent, or seven percent, or sixpercent, or five percent, or four percent, or three percent, or twopercent, or one percent.

The use of the term “at least one” will be understood to include one aswell as any quantity more than one, including but not limited to, 1, 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term “at least one” mayextend up to 100 or 1000 or more depending on the term to which it isattached. In addition, the quantities of 100/1000 are not to beconsidered limiting as lower or higher limits may also producesatisfactory results. In addition, the use of the term “at least one ofX, Y, and Z” will be understood to include X alone, Y alone, and Zalone, as well as any combination of X, Y, and Z. The use of ordinalnumber terminology (i.e., “first”, “second”, “third”, “fourth”, etc.) issolely for the purpose of differentiating between two or more items and,unless otherwise stated, is not meant to imply any sequence or order orimportance to one item over another or any order of addition.

As used herein, the words “comprising” (and any form of comprising, suchas “comprise” and “comprises”), “having” (and any form of having, suchas “have” and “has”), “including” (and any form of including, such as“includes” and “include”) or “containing” (and any form of containing,such as “contains” and “contain”) are inclusive or open-ended and do notexclude additional, unrecited elements or method steps. The term “orcombinations thereof” as used herein refers to all permutations andcombinations of the listed items preceding the term. For example, “A, B,C, or combinations thereof” is intended to include at least one of: A,B, C, AB, AC, BC, or ABC and, if order is important in a particularcontext, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing withthis example, expressly included are combinations that contain repeatsof one or more item or term, such as BB, AAA, MB, BBC, AAABCCCC, CBBAAA,CABABB, and so forth. The skilled artisan will understand that typicallythere is no limit on the number of items or terms in any combination,unless otherwise apparent from the context.

The term “each independently selected from the group consisting of”means when a group appears more than once in a structure, that group maybe selected independently each time it appears.

The term “hydrocarbyl” refers to a straight-chain, branched-chain, orcyclic, mono-, di-, or polyvalent group having hydrogen and carbon atomswith or without additional atom(s) of different kind(s). The additionalatom(s) may include one or more heteroatom(s).

The term “alkyl” refers to a functionalized or unfunctionalized,monovalent, straight-chain, branched-chain, or cyclic hydrocarbyl groupoptionally having one or more heteroatoms. Non-limiting examples ofalkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl,2-ethylhexyl, tert-octyl, iso-norbornyl, n-dodecyl, tert-dodecyl,n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl. The definition ofalkyl includes aryl groups, non-limiting examples of which includephenyl, tolyl, xylyl, naphthyl, and the like. The definition of alkylalso includes heteroaryl groups, non-limiting examples of which includepyridinyl, pyridazinyl, pyrimidyl, pyrazyl, triazinyl, pyrrolyl,pyrazolyl, imidazolyl, (1,2,3,)- and (1,2,4)-triazolyl, pyrazinyl,pyrimidinyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl,isoxazolyl, oxazolyl, and the like. The definition of alkyl alsoincludes combination(s) of non-aryl and aryl groups, non-limitingexamples of which include benzyl, phenylethyl, phenylpropyl,pyridinylmethyl, furylmethyl, and the like.

The term “alkylene” refers to a functionalized or unfunctionalized,divalent, straight-chain, branched-chain, or cyclic hydrocarbyl groupoptionally having one or more heteroatoms. Non-limiting examples ofalkylene groups include —CH₂—. —CH(CH₃)—, —C(CH₃)₂—, —CH₂—CH₂—,—CH(CH₃)—CH₂—, —CH₂—CH(CH₃)—, —C(CH₃)₂—CH₂—, —CH₂—C(CH₃)₂—,—CH(CH₃)—CH(CH₃)—, —C(CH₃)₂—C(CH₃)₂—, —CH₂—CH₂—CH₂—, —CH(CH₃)—CH₂—CH₂—,—CH₂—CH(CH₃)—CH₂—, —CH₂—CH₂—CH(CH₃)—, —CH₂—CH₂—CH₂—CH₂—,—CH₂—CH₂—CH₂—CH₂—CH₂—, —CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—,—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—, and

The definition of alkylene includes arylene groups, non-limitingexamples of which include phenylene, tolylene, xylylene, and the like.The definition of alkylene also includes heteroarylene groups,non-limiting examples of which include pyridinylene, pyridazinylene,pyrimidylene, pyrazylene, triazinylene, pyrrolylene, pyrazolylene,imidazolylene, (1,2,3,)- and (1,2,4)-triazolylene, pyrazinylene,pyrimidinylene, tetrazolylene, furylene, thienylene, isoxazolylene,thiazolylene, isoxazolylene, oxazolylene, and the like. The definitionof alkylene also includes combination(s) of non-arylene and arylenegroups.

The term “heteroatom” refers to oxygen, nitrogen, sulfur, silicon,phosphorous, and/or halogen. The heteroatom(s) may be present as a partof one or more heteroatom-containing functional groups. Non-limitingexamples of heteroatom-containing functional groups include ether,hydroxy, epoxy, carbonyl, amide, ester, carboxylic acid, imine, imide,amine, sulfonic acid, sulfonamide, phosphonic acid, and silane groups.

The term “functionalized” refers to the state of a moiety that has oneor more functional groups introduced to it by way of one or morefunctionalization reactions known to a person having ordinary skill inthe art. Non-limiting examples of functionalization reactions includeepoxidation, etherification, sulfonation, hydrolysis, amidation,esterification, hydroxylation, dihyroxylation, amination, ammonolysis,acylation, nitration, oxidation, dehydration, elimination, hydration,dehydrogenation, hydrogenation, acetalization, halogenation,dehydrohalogenation, Michael addition, aldol condensation, Canizzaroreaction, Mannich reaction, Clasien condensation, Suzuki coupling, andthe like.

The term “unfunctionalized” refers to the state of a moiety that is notfunctionalized.

The term “residue of” refers to a fragment of a reactant that remainsafter a reaction with another reactant(s). The residue may be mono-, di-or polyvalent.

The term “monomer” refers to a low molecular weight compound that iscapable of chemically bonding during polymerization with one or morecompounds of the same or different kind(s) to form a polymer.

The term “polymer” refers to a high molecular weight compound having oneor more types of monomer residues (repeating units) connected bycovalent chemical bonds. By this definition, polymers include compoundswherein the number of monomer units may range from very few, which morecommonly may be called as oligomers, to very many. Non-limiting types ofpolymers include homopolymers, and non-homopolymers such as copolymers,terpolymers, tetrapolymers and the higher analogues. A polymer may havea random, block, and/or alternating architecture.

The term “homopolymer” refers to a polymer that is formed from a singletype of monomer.

The term “non-homopolymer” refers to a polymer that is formed from twoor more different types of monomers. A non-homopolymer could be acopolymer, a terpolymer, or a higher analogue.

The term “copolymer” refers to a non-homopolymer that is formed from twodifferent types of monomers.

The term “terpolymer” refers to a non-homopolymer that is formed fromthree different types of monomers.

The term “non-crosslinked polymer” refers to a polymer that is notcrosslinked.

The term “branched” refers to any non-linear molecular structure. Theterm includes both branched and hyper-branched structures.

The term “free radical addition polymerization initiator” refers to acompound used in a catalytic amount to initiate a free radical additionpolymerization.

The term “alkyl (meth) acrylate” refers to an alkyl ester of acrylicand/or methacrylic acid.

The term “alkyl (meth) acrylamide” refers to an alkyl amide of acrylicand/or methacrylic acid.

The term “personal care composition” refers to any composition orformulation intended for use on and/or in the human body. The definitionincludes cosmetic compositions. Non-limiting examples of personal carecompositions include sun care compositions, after-sun compositions, haircare compositions, conditioning compositions, skin care compositions,oral care compositions, face care compositions, lip care compositions,eye care compositions, body care compositions, nail care compositions,anti-aging compositions, insect repellants, deodorant compositions,color cosmetic compositions, color-protection compositions, self-tanningcompositions, and foot care compositions.

The term “relative humidity” (abbreviated as RH) of an air-water mixturerefers to the ratio of the partial pressure of water vapor in themixture to the equilibrium vapor pressure of water at a giventemperature. Relative humidity is normally expressed as a percentage.The higher the percentage, the more humid the atmosphere.

The term “rheology” refers to the study of flow and deformation inmaterials. Particularly, it refers to the study of force and deformationin materials, such as, for example liquids. Further insight to the fieldof rheology may be found in the book ‘Rheology: Principles,Measurements, and Applications’ by C. W. Macosko that is hereinincorporated in its entirety by reference.

All percentages, ratio, and proportions used herein are based on aweight basis unless other specified.

In a first aspect, the invention provides a personal care compositioncomprising a polymer having the structure

wherein each Q is a hydrocarbyl moiety comprising at least one hydroxyland optionally at least one ether; each R₁ is a functionalized orunfunctionalized alkyl; a is a value ranging from about 0.1 to 100percent by weight of the polymer; and each b and c is an independentlyselected value ranging from 0 to about 99.9 percent by weight of thepolymer, with the proviso that the sum of a, b and c for the polymerequals 100 weight percent.

In a particular embodiment, each R₁ is a functionalized orunfunctionalized C₁-C₄ alkyl. More particularly, each R₁ isindependently selected from the group consisting of methyl, ethyl,propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and combinationsthereof. Even more particularly, each R₁ is independently selected fromthe group consisting of methyl and ethyl. Most particularly, each R₁ ismethyl.

In a particular embodiment, each Q is a hydrocarbyl moiety comprisingfrom about 3 to about 40 carbons, at least one hydroxyl, and optionallyat least one ether moiety. More particularly, each Q is a hydrocarbylmoiety comprising from about 3 to about 30 carbons, at least onehydroxyl, and optionally at least one ether moiety. Even more partparticularly, each Q is a hydrocarbyl moiety comprising from 3 to about20 carbons, at least one hydroxyl, and optionally at least one ethermoiety.

In particular embodiments, the number of ether moieties in each Q moietymay vary from one to about 30. More particularly, the number of ethermoieties in each Q moiety may vary from one to about 15. Even moreparticularly, the number of ether moieties in each Q moiety may varyfrom one to about 10. Most particularly, the number of ether moieties ineach Q moiety may vary from one to about 5.

In particular embodiments, the number of hydroxyl moieties in each Qmoiety may vary from one to about 30. More particularly, the number ofhydroxyl moieties in each Q moiety may vary from one to about 15. Evenmore particularly, the number of hydroxyl moieties in each Q moiety mayvary from one to about 10. Most particularly, the number of hydroxylmoieties in each Q moiety may vary from one to about 5.

Particularly, each Q has a structure independently selected from thegroup consisting of:

and combinations thereof, wherein each asterisk symbol (*) denotes thepoint of attachment of Q to the polymer backbone.

For the polymers described herein, a is a value ranging from about 0.1to 100 percent by weight of the polymer, and each b and c is anindependently selected value ranging from 0 to about 99.99 percent byweight of the polymer, with the proviso that the sum of a, b and c foreach polymer equals 100 weight percent.

Particularly, a is a value ranging from about 0.1 to 100 percent byweight of the polymer. More particularly, a is a value ranging fromabout 0.1 to about 50 percent by weight of the polymer. Even moreparticularly, a is a value ranging from about 0.1 to about 25 percent byweight of the polymer.

Particularly, each b and c is an independently selected value rangingfrom 0 to about 75 percent by weight of the polymer. More particularly,each b and c is an independently selected value ranging from 0 to about50 percent by weight of the polymer. Even more particularly, each b andc is an independently selected value ranging from 0 to about 25 percentby weight of the polymer.

In particular embodiments, the polymer that is a constituent of personalcare compositions according to the invention has a structure selectedfrom the group consisting of:

wherein a is a value ranging from about 0.1 to 100 percent by weight ofthe polymer, and each b and c for each polymer is an independentlyselected value ranging from 0 to about 99.9 percent by weight of thepolymer, with the proviso that the sum of a, b, and c for each polymerequals 100 weight percent.

Non-limiting examples of personal care compositions that may comprisepolymer(s) according to the invention include sun care compositions,after-sun compositions, hair care compositions, conditioningcompositions, skin care compositions, oral care compositions, face carecompositions, lip care compositions, eye care compositions, body carecompositions, nail care compositions, anti-aging compositions, insectrepellants, deodorant compositions, color cosmetic compositions,color-protection compositions, self-tanning compositions, and foot carecompositions. Particularly, the personal care composition is a hair carecomposition.

Particular, yet non-limiting applications of hair care compositionsaccording to the invention include: hairstyle retention at high relativehumidity, hair styling, hair setting, hair sculpting, hair curling, hairholding, hair waving, hair fixing, hair maintaining, hair shaping, hairstraightening, hair volumizing, hair relaxing, shampooing, hairconditioning, hair cleansing, promoting hair style durability, impartinghumidity resistance to hair and hair styles, enhancing hair shine,repairing split ends of hair, enhancing hair manageability such aslightness, smoothness, softness, disentangling and/or suppleness ofhair, modulating hair stylability, protecting hair from thermal damage,hair dyeing, hair coloring, hair bleaching, oxidation dyeing of hair,limiting hair color bleeding, protecting hair color, hair treating(e.g., anti-dandruff), anti-hair fall, and/or protecting hair from UVradiation.

Particular, yet non-limiting examples of hair care compositions includeshampoos, conditioners, aerosols, mousses, sprays, mists, gels, waxes,creams, lotions, glues, pomades, spritzes, solutions, oils, liquids,solids, W/O emulsions, O/W emulsions, suspensions, multiple emulsions,microemulsions, microencapsulated products, sticks, balms, tonics,pastes, reconstitutable products, nanoemulsions, solid lipidnanoparticles, liposomes, cubosomes, neosomes, putties, lacquers,serums, perms, volumizers, packs, flakes, 2-in-1 shampoo/conditionerproducts, and 3-in-1 shampoo/conditioner/styling products.

The hair care compositions according to the invention may also take theform of after-shampoo compositions, to be rinsed off or not, forpermanents, straightening, waving, dyeing, or bleaching, or the form ofrinse compositions to be applied before or after dyeing, bleaching,permanents, straightening, relaxing, waving or even between the twostages of a permanent or straightening process.

In particular embodiments, the hair care composition according to theinvention is a hair styling composition. Particular, yet non-limitingexamples of hair styling compositions include hair styling gels,aerosols, sprays, spritzes, lotions, creams, and mousses. Moreparticularly, the hair styling composition is a hair styling gel.

In particular embodiments, the hair styling compositions according tothe invention provide hairstyle retention to hair at a relative humidityexceeding about 40%. More particularly, the hair styling compositionsprovide hairstyle retention to hair at a relative humidity exceedingabout 60%. Even more particularly, the hair styling compositions providehairstyle retention to hair at a relative humidity exceeding about 80%.Most particularly, the hair styling compositions provide hairstyleretention to hair at a relative humidity of about 90% at a temperatureof about 80° F.

The hair care compositions according to the invention may furthercomprise one or more additives. Particular, yet non-limiting examples ofadditives include skin care or hair care agents, hair styling agents,hair fixative agents, film formers, structurants, gelling agents,surfactants, thickeners, preservatives, viscosity modifiers,electrolytes, pH adjusting agents, perfumes, dyes, organosiliconcompounds, anti-dandruff agents, anti-foaming agents, anti-frizz agents,penetrants, vitamins, conditioning agents, chelating agents,antimicrobial agents, preservatives, UV absorbers, sunscreens,anti-oxidants, anti-radical protecting agents, natural extracts,propellants, carriers, diluents, solvents, pharmaceutical actives,lubricants, combing aids, plasticizers, solubilizers, neutralizingagents, vapor pressure suppressants, bleaching agents, hydrating agents,moisturizers, pharmaceutically or cosmetically acceptable adjuvantsand/or additives, protectants, and combinations thereof.

Non-limiting examples of suitable UV actives include: octyl salicylate;pentyl dimethyl PABA; octyl dimethyl PABA; benzophenone-1;benzophenone-6; 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol;ethyl-2-cyano-3,3-diphenylacrylate; homomenthyl salicylate;bis-ethylhexyloxyphenol methoxyphenyl triazine;methyl-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate;2-(2H-benzotriazole-2-yl)-4-methylphenol; diethylhexyl butamidotriazone; amyl dimethyl PABA; 4,6-bis(octylthiomethyl)-o-cresol; CASnumber 65447-77-0; red petroleum; ethylhexyl triazone; octocrylene;isoamyl-p-methoxycinnamate; drometrizole; titanium dioxide;2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol;2-hydroxy-4-octyloxybenzophenone; benzophenone-2; diisopropylmethylcinnamate; PEG-25 PABA;2-(1,1-dimethylethyl)-6-[[3-(1,1-demethylethyl)-2-hydroxy-5-methylphenyl]methyl-4-methylphenylacrylate; drometrizole trisiloxane; menthyl anthranilate; butylmethoxydibenzoylmethane; 2-ethoxyethyl p-methoxycinnamate; benzylidenecamphor sulfonic acid; dimethoxyphenyl-[1-(3,4)]-4,4-dimethyl1,3-pentanedione; zinc oxide;N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)];pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];2,6-di-tert-butyl-4-[4,6-bis(octylthio)-1,3,5-triazin-2-ylamino]phenol;2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol;trolamine salicylate; diethylanolamine p-methoxycinnamate;polysilicone-15; CAS number 152261-33-1; 4-methylbenzylidene camphor;bisoctrizole; n-phenyl-benzenamine; reaction products with2,4,4-trimethylpentene; sulisobenzone;(2-ethylhexyl)-2-cyano-3,3-diphenylacrylate; digalloyl trioleate;polyacrylamido methylbenzylidene camphor; glyceryl ethylhexanoatedimethoxycinnamate;1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis-{[(2′-cyano-bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate;benzophenone-5;1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione;hexamethylendiamine; benzophenone-8; ethyl-4-bis(hydroxypropyl)aminobenzoate;6-tert-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenol;p-aminobenzoic acid;3,3′,3″,5,5′,5″-hexa-tert-butyl-α-α′-α″-(mesitylene-2,4,6-triyl)tri-p-cresol;lawsone with dihydroxyacetone; benzophenone-9; benzophenone-4;ethylhexyl dimethoxy benzylidene dioxoimidazoline propionate;N,N′-bisformyl-N,N′-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-;3-benzylidene camphor; terephthalylidene dicamphor sulfonic acid;camphor benzalkonium methosulfate; bisdisulizole disodium; etocrylene;ferulic acid;2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol;4,6-bis(dodecylthiomethyl)-o-cresol; β-2-glucopyranoxy propyl hydroxybenzophenone; phenylbenzimidazole sulfonic acid; benzophenone-3;diethylamine hydroxybenzoyl hexylbenzoate;3′,3′-diphenylacryloyl)oxy]methyl}-propane; ethylhexylp-methoxycinnamate, and blends thereof.

Non-limiting examples of suitable antioxidants and/or antiradicalprotecting agents include: BHA (tert-butyl-4-hydroxy anisole), BHT(2,6-di-tert-butyl-p-cresol), TBHQ (tert-butyl hydroquinone),polyphenols such as proanthocyanodic oligomers, flavonoids, hinderedamines such as tetra amino piperidine, erythorbic acid, polyamines suchas spermine, cysteine, glutathione, superoxide dismutase, lactoferrin,and blends thereof.

Non-limiting examples of structurants that may be used in the hair carecompositions according to the invention include dextrin palmitate,trihydroxystearin, hydroxy stearic acid, hydrophilic or hydrophobicsilica, hydrophobically modified clay selected from the group consistingof stearalkonium hectorite, quaternium-18 bentonite, quaternium-18hectorite, disteardimonium hectorite, derivatives thereof, and mixturesthereof.

The hair care compositions according to the invention may additionallycomprise one or more secondary hair styling agents, hair fixativeagents, and/or film formers.

Particularly useful as secondary hair styling agents are hair stylingpolymers. The hair styling polymers may be cationic, anionic, amphotericor nonionic in nature. The polymers may be synthetic or naturallyderived. Non-limiting examples of hair styling polymers include thefollowing polymer products available for sale from Ashland SpecialtyIngredients: (1) Cationic styling polymers with hair conditioningbenefits—Styleze™ W Polymer, Styleze™ CC-10 (pseudo cationic), Gafquat™755 NP, and Gafquat™ 440; (2) Styling polymers with excellent highhumidity curl retention—Styleze™ 2000, Allianz™ LT 120, Styleze™ WPolymer, and Advantage™ LCA; (3) Non-ionic styling polymers with broadingredient compatibility—Polyvinylpyrrolidones such as PVP K-30, PVPK-60 and PVP K-90, Vinylpyrrolidone/vinyl acetate copolymers such asPVP/VA (E, I or W) 735, PVP/VA (E or W) 635, PVP/VA (E or I) 535, PVP/VA(E or I) 335 and PVP/VA S-630, andpoly(vinylpyrrolidone/dimethylaminoethylmethacrylate) polymers such asCopolymer 845/937. Additional details on the aforementioned polymers andmethods of use, or compositions thereof, may be found in a publicationfrom Ashland Specialty Ingredients titled “A Composition Guide forExcellent Hair Styling Gels and Lotions” (2002) that is herebyincorporated in its entirety by reference.

A non-limiting example of hair fixative agent that may be used in haircare compositions according to the invention includes a hair fixativepolymer available for sale from Ashland Specialty Ingredients,AquaStyle™ 300 (INCI name Polyquaternium-69). A related publication fromAshland Specialty Ingredients titled “Aquastyle® 300, A Fixative Polymerwith Enhanced Styling Benefits” (2007) is hereby incorporated in itsentirety by reference.

Non-limiting examples of film formers that may be used in hair carecompositions according to the invention include film forming polymersavailable for sale from Ashland Specialty Ingredients such as (1)Aquaflex™ FX 64, (2) AquaCat™ clear cationic solution, (3) Aqualon™carboxymethylcellulose, (4) Klucel™ hydroxypropylcellulose, and (5)Primaflo™ HP22 polymer solution.

Further details on hair styling agents, hair fixative agents, and/orfilm formers may be found in U.S. Pat. Nos. 7,871,600, 7,205,271,7,122,175, 7,041,281, 6,998,114, 6,749,836, 6,689,346, 6,599,999,6,562,325, 6,413,505, 6,387,351, 6,228,352, 5,643,581, 5,922,312,5,897,870, 5,879,669, 5,709,850, 5,753,216 and 5,632,977 each of whichis hereby incorporated in its entirety by reference.

Non-limiting examples of anti-frizz agents that may be used in hair carecompositions according to the invention include anti-frizz polymersavailable for sale from Ashland Specialty Ingredients such as AquaStyle™300 and Styleze™ XT3. Information on related anti-frizz agents may befound in U.S. Pat. Nos. 7,914,773, 7,785,575, and U.S. publishedapplication 2010/00093584, the disclosures of each of which is herebyincorporated in its entirety by reference.

One or more plasticizers or coalescing agents may be added to modify thefilm forming characteristics of hair care compositions according to theinvention. Non-limiting examples of plasticizers include glycols, adipicesters, phthalate esters, isobutyrate esters, terephthalate esters,epoxidized butyl esters or fatty acids, epoxidized vegetable oils,glycerine, di-2-ethylhexyladipate or dioctyladipate (DOA),di-2-ethylhexyl phthalate or dioctyl phthalate (DOP), di-2-ethylhexylterephthalate (DOTP), dicyclohexyl phthalate, diisononyl adipate,diisononylphthalate, n-butyl benzyl phthalate, 1,3-butyleneglycol/adipic acid polyester, dialkyl adipate, dialkyl phthalatederivatives where the alkyl group is a C₁-C₁₂ alkyl group,di-n-hexylazelate, diphenylphthalate, tricresol phosphate, benzylbenzoate, dibutyl phosphate, tributyl phosphate, tributoxyethylphosphate, triphenyl phosphate, butyl acetyl ricinoleate, glycerolacetyl ricinoleate, dibutyl phthalate, diethyl phthalate, dioctylphthalate, dimethoxyethyl phthalate, diisobutyl phthalate, diamylphthalate, dibutyl glycolate, butyl stearate, triethyl citrate, tributylcitrate, tributyl acetyl citrate, 2-hexyltriethylacetyl citrate, dibutyltartarate, camphor, epoxidized butyl esters of linseed oil fatty acids,epoxidized linseed oil, epoxidized soya oil, propylene glycol adipate,2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), methyl abietate,cumyl acetate, dibutoxyethyl adipate, di-n-hexylazalate,glyceryl-tri-benzerate, tri-n-butylcitrate, dioctyl fumarate, triisonyltrimellitate, dioctyl isophthalate, butyl oleate, chlorinated paraffin,tricresolphosphate, dibutyl sebacate, dimethicone copolyol (Dow Corning190), PEG-6 capric/caprylic glyceride (SOFTIGEN 767), DIACETIN,LAURAMIDE DEA (MONAMID 716), phenyl trimethicone (ABIL AV 20-1000),propylene glycol, dipropylene glycol, as well as polymeric plasticizers,and mixtures thereof. Non-limiting examples of coalescing solventsinclude acetone, methyl acetate, and di- or tri-propylene glycol methylethers, and mixtures thereof. Further examples of plasticizers may befound in U.S. Pat. Nos. 5,753,216 and 5,676,935, the disclosures of eachof which are hereby incorporated in its entirety by reference.

Non-limiting examples of propellants that may be used in hair carecompositions of the invention include trichlorofluoromethane,chlorodifluoromethane, 1,1-difluoroethane, dichlorotetrafluoroethane,monochlorodifluoromethane, trichlorotrifluoroethane, dimethyl ether,C₁-C₄ hydrocarbons such as methane, ethane, propane, n-butane, andisobutane, water-soluble gases such as, dimethyl ether, carbon dioxide,and/or nitrous oxide, and insoluble, compressed gases such as nitrogen,helium, and fully-fluorinated oxetanes and oxepanes, and mixturesthereof.

Non-limiting examples of penetrants that may be used in hair carecompositions of the invention include lanolin compounds, proteinhydrolysates, protein derivatives, and mixtures thereof.

Non-limiting examples of anti-foaming agents that may be used in haircare compositions of the invention include carrier oils, silicone oils,silicone foam inhibitors, hydrophobic silica, hydrophobic fatderivatives, waxes, water-insoluble polymers, amphiphilic components,emulsifiers, coupling agents, and mixtures thereof.

Any range of composition pH may be used. In aspects wherein thecomposition may be applied to keratinous material, the pH may range fromabout 2 to 12. The pH may be adjusted to a desired value by means ofadding one or more acidifying or alkalinizing agents that are well-knownin the state of the art. For example, the composition can contain atleast one alkalizing or acidifying agent in amounts from about 0.01% toabout 30% based on the total weight of the composition.

Non-limiting examples of acidifying or acidic pH adjusting agentsinclude organic acids, such as citric acid, acetic acid, carboxylicacids, α-hydroxyacids, β-hydroxyacids, α,β-hydroxyacids, salicylic acid,tartaric acid, lactic acid, glycolic acid, natural fruit acids, andcombinations thereof. In addition, inorganic acids, for examplehydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoricacid, and combinations thereof can be utilized.

Non-limiting examples of alkalizing or alkaline pH adjusting agentsinclude ammonia, alkali metal hydroxides (such as sodium hydroxide andpotassium hydroxide), ammonium hydroxide, alkanolamines (such as mono-,di- and triethanolamine), diisopropylamine, dodecylamine,diisopropanolamine, aminomethyl propanol, cocamine, oleamine,morpholine, triamylamine, triethylamine, tromethamine(2-amino-2-hydroxymethyl)-1,3-propanediol), andtetrakis(hydroxypropyl)ethylenediamine, hydroxyalkylamines andethoxylated and/or propoxylated ethylenediamines, alkali metal salts ofinorganic acids, such as sodium borate (borax), sodium phosphate, sodiumpyrophosphate, and the like, and mixtures thereof.

Non-limiting examples of alkalizing agent can be chosen from ammonia,alkali carbonates, alkanolamines, like mono-, di- and triethanolamines,as well as their derivatives, sodium or potassium hydroxides andcompounds of the following formula:

wherein R₁ may be a propylene residue that may be optionally substitutedwith an hydroxyl group or a C₁-C₄ alkyl radical; R₂, R₃, R₄ and R₅ areidentical or different and represent a hydrogen atom, a C₁-C₄ alkylradical or C₁-C₄ hydroxyalkyl radical.

The personal care compositions according to the invention mayadditionally comprise one or more buffers. Suitable buffering agentsinclude but are not limited to alkali or alkali earth carbonates,phosphates, bicarbonates, citrates, borates, acetates, acid anhydrides,succinates and the like, such as sodium phosphate, citrate, borate,acetate, bicarbonate, and carbonate.

The personal care compositions may be formulated in any of the productforms known to a person of ordinary skill in the art. Non-limitingproduct forms are described below.

Product Forms

Non-limiting sun care product forms include: solutions, liquids, creams,powders, lotions, gels, pastes, waxes, aerosols, sprays, mists,roll-ons, sticks, milks, emulsions, and wipes.

Non-limiting skin care product forms include: solutions, oils, lotions,creams, ointments, liquids, gels, solids, W/O emulsions, O/W emulsions,milks, suspensions, microemulsions, dispersions, microencapsulatedproducts, sticks, balms, tonics, pastes, mists, reconstitutableproducts, peels, soaps, aerosols, mousses, waxes, glues, pomades,spritzes, putties, lacquers, serums, perms, powders, pencils, flakes,blush, highlighters, bronzers, concealers, and 2-way cake products.

The compositions of the invention may also take the form of skin-washingcompositions, and particularly in the form of solutions or gels for thebath or shower, or of make-up removal products.

The six skin care product categories that follow next may be considereda subset of the skin and sun care products:

(1) Eye Care

Non-limiting eye care product forms include: mascaras, eye liners, eyeshadows, curlers of eye lashes, eyebrow pencils, and eye pencils.

(2) Lip Care

Non-limiting lip care product forms include: lipsticks, lip balms, lippencils, lip glosses, lip sprays, transparent lip bases, tinted lipmoisturizers, and multi-functional color sticks that can also be usedfor cheeks and eyes.

(3) Nail Care

Non-limiting nail care product forms include: nail polishes, nailvarnishes, enamels, nail varnish removers, home-manicure products suchas cuticle softeners and nail strengtheners, and artificial nails.

(4) Face Care

Non-limiting face care product forms include: creams, lotions,solutions, oils, liquids, peels, scrubs, emulsions, suspensions,microemulsions, microencapsulated product, pastes, reconstitutableproduct, aerosols, mousses, gels, waxes, glues, pomades, spritzes,facial wet-wipes, putties, lacquers, serums, perms, powders, blush,highlighters, bronzers, masks, and concealers.

(5) Body Care

Non-limiting body care product forms include: foams, peels, masks, gels,sticks, aerosols, lotions, salts, oils, balls, liquids, powders, peels,pearls, bar soaps, liquid soaps, body washes, cleansers, scrubs, creams,flakes, other bath and shower products, shaving products, waxingproducts, and sanitizers.

(6) Foot Care

Non-limiting foot care product forms include: mousses, creams, lotions,powders, liquids, sprays, aerosols, gels, flakes, and scrubs.

Non-limiting oral care product forms include: toothpastes, adhesives,gums, gels, powders, creams, solutions, lotions, liquids, dispersions,suspensions, emulsions, tablets, capsules, rinses, flosses, aerosols,strips, films, pads, bandages, microencapsulated products, syrups, andlozenges.

Also contemplated are personal care compositions comprising polymer(s)described herein complexed with iodine. These compositions may be usedin treating skin conditions, non-limiting examples of which includedermatitis, wounds, bacterial infections, burns, rashes, and herpes.These complexed compositions may be staining, substantiallynon-staining, or essentially non-staining.

Examples of related personal care compositions are disclosed in U.S.Pat. Nos. 5,599,800; 5,650,166; 5,916,549; and 6,812,192; U.S. patentapplication 2009/0317432; EP 556,660; 661,037; 661,038; 662,315;676,194; 796,077; 970,682; 976383; 1,415,654; and 2,067,467; and WO2005/032506; each of which is hereby incorporated in its entirety byreference.

It is also contemplated that the personal care compositions may be usedin products for male and/or female personal grooming and/or toiletrysuch as: sanitary napkins, baby diapers, adult diapers, feminineproducts, products for incontinence, and other related products.

An array of additional personal care compositions, methods, and uses arecontemplated. Disclosure of these compositions may be found in thefollowing brochures by Ashland Specialty Ingredients, each of which ishereby incorporated in its entirety by reference: Plasdone™ K-29/32,Advanced non-oxidative, non-abrasive teeth whitening in toothpastes,mouthwashes, and oral rinses (2010), Polymers for oral care, product andapplications guide (2002), A composition guide for excellent hairstyling gels and lotions (4/2003), PVP (polyvinylpyrrolidone) (no dateprovided), and Textile chemicals, solutions for the most challengingproduct environment (no date provided).

Also contemplated are additional personal care compositions that maycomprise the polymers described herein. Disclosures on such compositionsmay be found in the publications listed below, each of which is herebyincorporated in its entirety by reference: (1) PrototypeCompositions—Personal Care Products (2009) from Xiameter, Dow Corning.(2) Sun care compositions under the category “Refreshing Sun”, “YoungerSun”, “Sun for Men”, and “Sunny Glow” from Dow Corning. (3) CosmeticNanotechnology, Polymers and Colloids in Cosmetics, 2007, ACS SymposiumSeries. (4) Review Paper: Lipid nanoparticles (SLN, NLC) in cosmetic andpharmaceutical dermal products, International Journal of Pharmaceutics,Volume 366, 2009.

Optional: Additional Composition Ingredients

It is also contemplated that the personal care compositions optionallymay contain one or more additional ingredients.

Further, it is contemplated that the composition ingredients may beformulated in a single container, or the ingredients may be formulatedin-part in two or more distinct containers of the same or differenttype, the contents of which may require mixing prior to use.

Furthermore, it also is contemplated that the compositions may beprepared in the form of concentrates that may be diluted by a suitablesubstance(s) prior to use. The concentrate may, in turn, be present inany of the forms as described under ‘Product Forms’ for the personalcare compositions of the invention.

A non-limiting list of classes of additional ingredients that mayoptionally be present in different types of personal care compositionsis provided below: conditioning agents, antimicrobials, protectives (forexample, antiradical agents), abrasives, UV absorbers, emulsifiers(including, but not limited to ethoxylated fatty acids, ethoxylatedglyceryl esters, ethoxylated oils, ethoxylated sorbitan esters, fattyesters, PEG esters, polyglycerol esters), antiperspirants (including,but not limited to aluminium chlorohydrates, aluminium zirconiumchlorhydrates), antioxidants, vitamins and/or provitamins, botanicals,fixatives, oxidizing agents, reducing agents, dyes, cleansing agents,anionic, cationic, nonionic, and/or amphoteric surfactants, thickenersand/or gelling agents, perfumes, flavors, and/or fragrances, pearlizingagents, stabilizers, pH adjusters, filters, antimicrobial agents,preservatives and/or disinfectants, associative polymers, oils ofvegetable, mineral, and/or synthetic origin, polyols, silicones,colorants, bleaching agents, highlighting agents, propellants(including, but not limited to hydrocarbons, dimethyl ether,fluorocarbons), styling polymers, benefit agents, skin lighteners(including, but not limited to arbutin and kojic acids), tanning agents(including, but not limited to dihydroxyacetone), solvents and/orcosolvents, diluents, essential oils, sequestrants and/or chelators,carriers, and natural extracts and/or natural products.

The amount of each ingredient in the composition varies depending on thetype of composition, the function and/or physicochemical property of theingredient, and the amount of other co-ingredients. The precise amountof each ingredient may be easily determined by any person skilled in therelated arts.

It may be desirable to include one or more ingredients described in theprior art disclosures IPCOM000186541D, IPCOM000128968D, andIPCOM000109682D on www.ip.com, the contents of each of these disclosuresare hereby incorporated in their entirety by reference.

Further reference to formulary co-ingredients and product forms includethe disclosures in US 2010/0183532, paragraphs [0096]-[0162], and WO2010/105050, paragraphs [0053]-[0069], the contents of which are herebyincorporated in their entirety by reference.

Any known conditioning agent may be used in the personal carecompositions of the invention. An extensive discussion on conditioningagents may be found in the book Conditioning Agents for Skin and Hair,Cosmetic Science and Technology Series, Volume 21, 1999, Marcel DekkerPublishers. The contents of the book are hereby incorporated in itsentirety by reference.

Conditioning agents may be chosen from synthetic oils, mineral oils,vegetable oils, fluorinated or perfluorinated oils, natural or syntheticwaxes, silicones, cationic polymers, proteins and hydrolyzed proteins,cationic surfactants, ceramide type compounds, fatty amines, fatty acidsand their derivatives, as well as mixtures of these different types ofcompounds.

Non-limiting examples of suitable synthetic oils include: polyolefins,e.g., poly-α-olefins, such as polybutenes, polyisobutenes, polydecenes,and blends thereof. The polyolefins may be hydrogenated.

Non-limiting examples of suitable mineral oils include hexadecane andoil of paraffin.

Non-limiting examples of suitable animal and vegetable oils include:sunflower oil, corn oil, soy oil, avocado oil, jojoba oil, squash oil,raisin seed oil, sesame seed oil, walnut oil, fish oil, glyceroltricaprocaprylate, purcellin oil, liquid jojoba, and blends thereof.Also suitable are natural oils such as oils of eucalyptus, lavender,vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile, savory,nutmeg, cinnamon, hyssop, caraway, orange, geranium, cade, bergamot, andblends thereof.

The conditioning agent may be a fluorinated or a perfluorinated oil. Thefluoridated oils may also be fluorocarbons such as fluoramines, e.g.,perfluorotributylamine, fluoridated hydrocarbons such asperfluorodecahydronaphthalene, fluoroesters, fluoroethers, and blendsthereof.

Non-limiting examples of suitable natural and synthetic waxes include:carnauba wax, candelila wax, alfa wax, paraffin wax, ozokerite wax,vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax,absolute flower waxes such as black currant flower wax, animal waxessuch as bees wax, modified bees wax (cerabellina), marine waxes andpolyolefin waxes such as polyethylene wax, and blends thereof.

The conditioning agent may be any silicone known by those skilled in theart. Silicones include polyorganosiloxanes that are insoluble in thecomposition. The silicones may be present in the form of oils, waxes,resins, or gums. They may be volatile or non-volatile.

Non-limiting examples of suitable silicones include: polyalkylsiloxanes, polyaryl siloxanes, polyalkyl aryl siloxanes, silicone gumsand resins, polyorgano siloxanes modified by organofunctional groups,and blends thereof.

Suitable polyalkyl siloxanes include polydimethyl siloxanes withterminal trimethyl silyl groups or terminal dimethyl silanol groups(dimethiconol) and polyalkyl (C1-C20) siloxanes. Suitable polyalkyl arylsiloxanes include polydimethyl methyl phenyl siloxanes and polydimethyldiphenyl siloxanes. The siloxanes can have a linear or branchedstructure.

Suitable silicone gums include polydiorganosiloxanes, such as thosehaving a number-average molecular weight between 200,000 Da and1,000,000 Da used alone or mixed with a solvent.

Non-limiting examples of suitable silicone gums include: polymethylsiloxane, polydimethyl siloxane/methyl vinyl siloxane gums, polydimethylsiloxane/diphenyl siloxane, polydimethyl siloxane/phenyl methylsiloxane, polydimethyl siloxane/diphenyl siloxane/methyl vinyl siloxane,and blends thereof.

Non-limiting examples of suitable silicone resins include silicones witha dimethyl/trimethyl siloxane structure and resins of the trimethylsiloxysilicate type.

The organo-modified silicones suitable for use in the invention includesilicones such as those previously defined and containing one or moreorganofunctional groups attached by means of a hydrocarbon radical, andgrafted silicone polymers. The organo-modified silicones may be one fromthe amino functional silicone family.

The silicones may be used in the form of emulsions, nano-emulsions, ormicro-emulsions.

The cationic polymers that may be used as conditioning agents accordingto the invention generally have a molecular weight (average number) fromabout 500 Da to about 5,000,000 Da, and particularly from about 1,000 Dato about 3,000,000 Da. The expression “cationic polymer” as used hereinindicates any polymer having at least one cationic group.

The cationic polymers may be chosen from among polymers containingprimary, secondary, tertiary amine, and/or quaternary ammonium groupsthat may form part of the main polymer backbone and/or side chain(s).

Non-limiting examples of suitable cationic polymers include polyamines,polyaminoamides, and quaternary polyammonium classes of polymers, suchas:

(1) homopolymers and copolymers derived from acrylic or methacrylicesters or amides. The copolymers may contain one or more units derivedfrom acrylamides, methacrylamides, diacetone acrylamides, acrylic ormethacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinyl caprolactam, and vinyl esters. Non-limiting,specific examples include: copolymers of acrylamide and dimethyl aminoethyl methacrylate quaternized with dimethyl sulfate or with an alkylhalide; copolymers of acrylamide and methacryloyl oxyethyl trimethylammonium chloride; the copolymer of acrylamide and methacryloyl oxyethyltrimethyl ammonium methosulfate; copolymers of vinyl pyrrolidone anddialkylaminoalkyl acrylate or methacrylate, optionally quaternized, suchas the products sold under the name Gafquat™ by Ashland SpecialtyIngredients; terpolymers of dimethyl amino ethyl methacrylate, vinylcaprolactam, and vinyl pyrrolidone such as the product sold under thename Gaffix™ VC 713 by Ashland Specialty Ingredients; the vinylpyrrolidone/methacrylamidopropyl dimethylamine copolymer, marketed underthe name Styleze™ CC 10 by Ashland Specialty Ingredients; and the vinylpyrrolidone/quaternized dimethyl amino propyl methacrylamide copolymerssuch as the product sold under the name Gafquat™ HS 100 by AshlandSpecialty Ingredients (Wayne, N.J.).

(2) derivatives of cellulose ethers containing quaternary ammoniumgroups, such as hydroxy ethyl cellulose quaternary ammonium that hasreacted with an epoxide substituted by a trimethyl ammonium group.

(3) derivatives of cationic cellulose such as cellulose copolymers orderivatives of cellulose grafted with a hydrosoluble quaternary ammoniummonomer, as described in U.S. Pat. No. 4,131,576, such as hydroxy alkylcellulose, and hydroxymethyl-, hydroxyethyl- or hydroxypropyl-cellulosegrafted with a salt of methacryloyl ethyl trimethyl ammonium,methacrylamidopropyl trimethyl ammonium, or dimethyl diallyl ammonium.

(4) cationic polysaccharides such as described in U.S. Pat. Nos.3,589,578 and 4,031,307, guar gums containing cationic trialkyl ammoniumgroups, and guar gums modified by a salt, e.g., chloride of 2,3-epoxypropyl trimethyl ammonium.

(5) polymers composed of piperazinyl units and alkylene or hydroxyalkylene divalent radicals with straight or branched chains, possiblyinterrupted by atoms of oxygen, sulfur, nitrogen, or by aromatic orheterocyclic cycles, as well as the products of the oxidation and/orquaternization of such polymers.

(6) water-soluble polyamino amides prepared by polycondensation of anacid compound with a polyamine. These polyamino amides may bereticulated.

(7) derivatives of polyamino amides resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids followed by alkylationby bi-functional agents.

(8) polymers obtained by reaction of a polyalkylene polyamine containingtwo primary amine groups and at least one secondary amine group with adioxycarboxylic acid chosen from among diglycolic acid and saturateddicarboxylic aliphatic acids having 3 to 8 atoms of carbon. Suchpolymers include those described in U.S. Pat. Nos. 3,227,615 and2,961,347.

(9) cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammoniumsuch as the homopolymer of dimethyl diallyl ammonium chloride andcopolymers of diallyl dimethyl ammonium chloride and acrylamide.

(10) quaternary diammonium polymers such as hexadimethrine chloride.

(11) quaternary polyammonium polymers, including, for example, Mirapol®A 15, Mirapol® AD1, Mirapol® AZ1, and Mirapol® 175 products sold byMiranol.

(12) quaternary polymers of vinyl pyrrolidone and vinyl imidazole suchas the products sold under the names Luviquat® FC 905, FC 550, and FC370 by BASF Corporation.

(13) quaternary polyamines.

(14) reticulated polymers known in the art.

Other cationic polymers that may be used include cationic proteins orhydrolyzed cationic proteins, polyalkyleneimines such aspolyethyleneimines, polymers containing vinyl pyridine or vinylpyridinium units, condensates of polyamines and epichlorhydrins,quaternary polyurethanes, and derivatives of chitin.

The conditioning agent may comprise a protein or hydrolyzed cationic ornon-cationic protein. Non-limiting examples of suitable compoundsinclude: hydrolyzed collagens having triethyl ammonium groups,hydrolyzed collagens having trimethyl ammonium and trimethyl stearylammonium chloride groups, hydrolyzed animal proteins having trimethylbenzyl ammonium groups (benzyltrimonium hydrolyzed animal protein),hydrolyzed proteins having groups of quaternary ammonium on thepolypeptide chain, including at least one C1-C18 alkyl, and blendsthereof.

Non-limiting examples of suitable hydrolyzed cationic proteins include:Croquat® L, in which the quaternary ammonium groups include a C12 alkylgroup, Croquat® M, in which the quaternary ammonium groups includeC10-C18 alkyl groups, Croquat® S in which the quaternary ammonium groupsinclude a C18 alkyl group, Crotein® Q in which the quaternary ammoniumgroups include at least one C1-C18 alkyl group, and blends thereof.These products are sold by Croda.

The conditioning agent may also comprise quaternized vegetableprotein(s) such as wheat, corn, or soy proteins, non-limiting examplesof which include: cocodimonium hydrolyzed wheat protein, laurdimoniumhydrolyzed wheat protein, steardimonium hydrolyzed wheat protein,2-N-stearoyl amino-octadecane-1,3-diol, 2-N-behenoylamino-octadecane-1,3-diol,2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3,4-triol, n-stearoyl phytosphingosine, 2-N-palmitoylamino-hexadecane-1,3-diol, bis-(N-hydroxy ethyl n-cetyl) malonamide,n-(2-hydroxy ethyl)-N-(3-cetoxyl-2-hydroxy propyl) amide of cetylicacid, n-docosanoyl n-methyl-D-glucamine, and blends thereof.

The conditioning agent may also comprise a cationic surfactant such as asalt of a primary, secondary, or tertiary fatty amine, optionallypolyoxyalkylenated, a quaternary ammonium salt, a derivative ofimadazoline, or an amine oxide. Conditioning agents may also be selectedfrom the group consisting of: mono-, di-, and tri-alkyl amines, andquaternary ammonium compounds with a counterion such as a chloride, amethosulfate, a tosylate, etc. Non-limiting examples of suitable aminesinclude: cetrimonium chloride, dicetyldimonium chloride, behentrimoniummethosulfate, and blends thereof.

The conditioning agent may comprise a fatty amine. Non-limiting examplesof suitable fatty amines include: dodecyl amines, cetyl amines, stearylamines such as stearamidopropyl dimethylamine, and blends thereof.

The conditioning agent may comprise a fatty acid or derivative(s)thereof. Non-limiting examples of suitable fatty acids include: myristicacid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleicacid, isostearic acid, and blends thereof. The derivatives of fattyacids include carboxylic ester acids including mono-, di-, tri- andtetra-carboxylic acids esters, amides, anhydrides, esteramides, imides,and mixtures of these functional groups.

Also suitable as conditioning agents are the following commercialproducts:

(1) Aquacat™ Clear Cationic Solution (INCI Name: guarhydroxypropyltrimonium Chloride), n-Hance™ SP-100 (INCI Name:acrylamidopropyl trimonium chloride/acrylamide copolymer), and n-Hance™cationic guar (INCI Name: guar hydroxypropyltrimonium chloride) fromAshland Specialty Ingredients

(2) Salcare® from BASF Corp.

(3) Softcat™ Polymers from The Dow Chemical Company.

(4) Jaguar® C500, Polycare® Boost, Mackconditioner™ Brite, and Mackine®301 from Rhodia.

(5) Stepanquat® ML, Stepanquat® GA-90, Ninol®, and Ammonyx® from StepanCompany.

(6) Conditioneze™ 7 and Conditioneze™ NT-20 from Ashland SpecialtyIngredients (Wayne, N.J.).

Of course, mixtures of two or more conditioning agents may be used.

The conditioning agent(s) may be present in an amount from about 0.001%to about 20%, particularly from about 0.01% to about 10%, and even moreparticularly from about 0.1% to about 3% by weight of the composition.

Personal care compositions may optionally comprise antimicrobialagent(s).

Non-limiting examples of suitable water insoluble, non-cationicantimicrobial agents include: halogenated diphenyl ethers, phenoliccompounds including phenol and its homologs, mono and poly-alkyl andaromatic halophenols, resorcinol and its derivatives, bisphenoliccompounds and halogenated salicylanilides, benzoic esters, halogenatedcarbanilides, and blends thereof.

Non-limiting examples of suitable water soluble antimicrobial agentsinclude: quaternary ammonium salts, bis-biquanide salts, triclosanmonophosphate, and blends thereof.

The quaternary ammonium agents include those in which one or two of thesubstituents on the quaternary nitrogen has a carbon chain length(typically alkyl group) from about 8 to about 20, typically from about10 to about 18 carbon atoms, while the remaining substituents (typicallyalkyl or benzyl group) have a lower number of carbon atoms, such as fromabout 1 to about 7 carbon atoms, typically methyl or ethyl groups.

Non-limiting examples of suitable quaternary ammonium antibacterialagents include: Dodecyl trimethyl ammonium bromide, tetradecylpyridiniumchloride, domiphen bromide, n-tetradecyl-4-ethyl pyridinium chloride,dodecyl dimethyl(2-phenoxyethyl)ammonium bromide, benzyl dimethylstearylammonium chloride, cetyl pyridinium chloride, quaternized5-amino-1,3-bis(2-ethyl-hexyl)-5-methyl hexahydropyrimidine,benzalkonium chloride, benzethonium chloride, methyl benzethoniumchloride, and blends thereof.

Other antimicrobial compounds are bis[4-(R-amino)-1-pyridinium]alkanesas disclosed in U.S. Pat. No. 4,206,215. Other antimicrobials such ascopper salts, zinc salts and/or stannous salts may also be included.Also useful are enzymes, including endoglycosidase, papain, dextranase,mutanase, and blends thereof. Such antimicrobial agents are disclosed inU.S. Pat. Nos. 2,946,725 and 4,051,234. The antimicrobial agents mayalso comprise chlorhexidine, triclosan, and flavor oils such as thymol.Triclosan and other agents are disclosed in U.S. Pat. Nos. 5,015,466 and4,894,220.

In particular aspects, one or more preservatives may be included.

Non-limiting examples of suitable preservatives include: benzoic acid,sorbic acid, dehydroacetic acid, diazolidinyl ureas, imidazolidinylureas, salicylic acid, piroctone olamine, DMDM hydantoin, IPBC(iodopropynyl butylcarbamate), triclosan, bronopol, formaldehyde,isothiazolinones, nitrates/nitrites, parabens, phenoxyethanol, potassiumsorbate, sodium benzoate, sulphites, sulphur dioxide, and blendsthereof.

In particular aspects, preservative boosters/solvents may beincorporated, non-limiting examples of which include: caprylyl glycol,hexylene glycol, pentylene glycol, ethylhexylglycerin, caprylhydroxamicacid, caprylohydroxamic acid, glyceryl caprylate, and blends thereof.

Polysaccharides, such as gum Arabic, may be included as well.

Personal care compositions may comprise liquid or liquid-like carrier(s)that help to distribute, disperse, and/or dissolve the ingredients.

Non-limiting examples of suitable liquid carriers include: water,alcohols, oils, esters, and blends thereof.

The compositions of the invention may also be in the form of aqueous orhydro-alcoholic solutions.

The physiological and cosmetically acceptable medium may consistexclusively of water, a cosmetically acceptable solvent, or a blend ofwater and a cosmetically acceptable solvent, such as a lower alcoholcomposed of C1 to C4, such as ethanol, isopropanol, t-butanol,n-butanol, alkylene glycols such as propylene glycol, and glycol ethers.

Personal care compositions may comprise vitamin(s), provitamin(s),and/or mineral(s).

Non-limiting examples of suitable vitamins include: ascorbic acid(vitamin C), vitamin E, vitamin E acetate, vitamin E phosphate, Bvitamins such as B3 and B5, niacin, vitamin A, derivatives thereof, andblends thereof.

Non-limiting examples of suitable provitamins include: panthenol,retinol, and blends thereof.

Non-limiting examples of suitable minerals include: talc, clay, calciumcarbonate, silica, kaolin, mica, and blends thereof. Further examples ofminerals that may be used in the personal care compositions may be foundin a brochure titled Minerals for personal care from Imerys PerformanceMinerals, the disclosure of which is hereby incorporated in its entiretyby reference.

Personal care compositions may comprise one or more surfactants.Surfactants serve in solubilizing, dispersing, emulsifying and/orreducing the interfacial tension. Surfactants may be chosen fromanionic, nonionic, amphoteric, zwitterionic, or cationic surfactants, orblends thereof.

Anionic surfactants useful herein include the water-soluble salts ofalkyl sulfates having from 8 to 20 carbon atoms in the alkyl radical(e.g., sodium alkyl sulfate) and the water-soluble salts of sulfonatedmonoglycerides of fatty acids having from 8 to 20 carbon atoms. Sodiumlauryl sulfate (SLS) and sodium coconut monoglyceride sulfonates arenon-limiting examples of anionic surfactants of this type.

Non-limiting examples of suitable anionic surfactants include:sarcosinates, taurates, isethionates, sodium lauryl sulfoacetate, sodiumlaureth carboxylate, and sodium dodecyl benzenesulfonate. Also suitableare alkali metal or ammonium salts of surfactants such as the sodium andpotassium salts of the following: lauroyl sarcosinate, myristoylsarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate, and oleoylsarcosinate.

Non-limiting examples of suitable cationic surfactants include:derivatives of aliphatic quaternary ammonium compounds having at leastone long alkyl chain containing from about 8 to about 18 carbon atoms,such as, lauryl trimethylammonium chloride, cetyl pyridinium chloride,cetyl trimethylammonium bromide,di-isobutylphenoxyethyl-dimethylbenzylammonium chloride, coconutalkyltrimethylammonium nitrite, cetyl pyridinium fluoride, and blendsthereof. Further suitable are quaternary ammonium fluorides havingdetergent properties such as compounds described in U.S. Pat. No.3,535,421. Certain cationic surfactants may act as germicides in thecompositions disclosed herein.

Nonionic surfactants useful herein include compounds produced by thecondensation of alkylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound which may be aliphatic or alkylaromatic innature.

Non-limiting examples of suitable nonionic surfactants include:poloxamers (sold under the trade name Pluronic® by BASF Corporation),polyethylene oxide condensates of alkyl phenols, products derived fromthe condensation of ethylene oxide with the reaction product ofpropylene oxide and ethylene diamine, ethylene oxide condensates ofaliphatic alcohols, long chain tertiary amine oxides, long chaintertiary phosphine oxides, long chain dialkyl sulfoxides, and blendsthereof.

Non-limiting examples of suitable zwitterionic surfactants includebetaines and derivatives of aliphatic quaternary ammonium compounds inwhich the aliphatic radicals can be straight chain or branched, andwhich contain an anionic water-solubilizing group, e.g., carboxy,sulfonate, sulfate, phosphate, or phosphonate.

Non-limiting examples of suitable betaines include: decyl betaine or2-(N-decyl-N,N-dimethylammonio)acetate, coco betaine or2-(N-coc-N,N-dimethyl ammonio)acetate, myristyl betaine, palmitylbetaine, lauryl betaine, cetyl betaine, stearyl betaine, and blendsthereof. The amidobetaines are exemplified by cocoamidoethyl betaine,cocoamidopropyl betaine, lauramidopropyl betaine, and the like. Thebetaines of choice include cocoamidopropyl betaines such aslauramidopropyl betaine. Suitable betaine surfactants are disclosed inU.S. Pat. No. 5,180,577.

Other surfactants such as fluorinated surfactants may also beincorporated within the compositions of the invention.

Also suitable as surfactants are the following commercial products:

(1) Alkanolamides, under the trade names Amidex™ and Schercomid™;amido-amines, under the trade names Katemul™ and Schercodine™; amineoxides, under the trade names Chemoxide™ and Schercamox™; amphoterics,under the trade names Chembetaine™, Schercotaine™ and Schercoteric™;imidazolines, under the trade name Schercozoline™; pearlizing agents,under the trade name Quickpearl™; performance concentrates, under thetrade names Sulfochem™ and Chemoryl™; soaps (potassium cocoate andpotassium soyate); specialty ethoxylates, under the trade nameChemonic™; specialty quats under the trade names Quatrex™ andSchercoquat™; sulfates, under the trade name Sulfochemr™; andsulfosuccinates, under the trade name Chemccinate™ from Lubrizol.

(2) Avaniel, Cremaphore®, Jordapan®, and Pluracare® from BASF Corp.

(3) Miracare® SLB, Mackam® Bab, Mackanate® Ultra SI, Miranol® Ultra, andMiracare® Plaisant from Rhodia.

(4) Stepan® Pearl 2, Stepan® Pearl 4, Stepan® Pearl Series, Neobee®M-20, Stepan® PTC, Amphosol® 2CSF, Steol®, Stepan-Mild® GCC, Stepan®SLL-FB, Stepanol® AM, Stepanol® PB, Alpha-Step® BSS-45, Bio-Terge® 804,Stepan-Mild® L3, Stepan® SLL-FB, Stepan® SSL-CG, and Stepanol® CFAS-70from Stepan Company.

Also suitable as surfactants are those described in the book Surfactantsin Personal Care Products and Decorative Cosmetics, Third Edition, 2006,CRC Press. The disclosure is incorporated hereby in its entirety byreference.

Personal care compositions may be also be formulated as detergentcompositions, such as shampoos, bath gels, and bubble baths. Suchcompositions comprise water as a liquid carrier. The surfactant orsurfactants that form the washing base may be chosen alone or in blends,from known anionic, amphoteric, zwitterionic and/or non-ionicsurfactants. The quantity and quality of the washing base must besufficient to impart a satisfactory foaming and/or detergent value tothe final composition. The washing base may be present in an amount fromabout 4% to about 50% by weight, particularly from about 6% to about 35%by weight, and more particularly from about 8% to about 25% by weight ofthe final composition.

Personal care compositions may comprise one or more thickener(s) and/orviscosifier(s).

Non-limiting examples of suitable thickeners and/or viscosifiersinclude: Acetamide MEA; acrylamide/ethalkonium chloride acrylatecopolymer; acrylamide/ethyltrimonium chloride acrylate/ethalkoniumchloride acrylate copolymer; acrylamides copolymer; acrylamide/sodiumacrylate copolymer; acrylamide/sodium acryloyldimethyltaurate copolymer;acrylates/acetoacetoxyethyl methacrylate copolymer;acrylates/beheneth-25 methacrylate copolymer; acrylates/C10-C30 alkylacrylate crosspolymer; acrylates/ceteth-20 itaconate copolymer;acrylates/ceteth-20 methacrylate copolymer; acrylates/laureth-25methacrylate copolymer; acrylates/palmeth-25 acrylate copolymer;acrylates/palmeth-25 itaconate copolymer; acrylates/steareth-50 acrylatecopolymer; acrylates/steareth-20 itaconate copolymer;acrylates/steareth-20 methacrylate copolymer; acrylates/stearylmethacrylate copolymer; acrylates/vinyl isodecanoate crosspolymer;acrylic acid/acrylonitrogens copolymer; adipic acid/methyl DEAcrosspolymer; agar; agarose; alcaligenes polysaccharides; algin; alginicacid; almondamide DEA; almondamidopropyl betaine; aluminum/magnesiumhydroxide stearate; ammonium acrylates/acrylonitrogens copolymer;ammonium acrylates copolymer; ammonium acryloyldimethyltaurate/vinylformamide copolymer; ammonium acryloyldimethyltaurate/VP copolymer;ammonium alginate; ammonium chloride; ammonium polyacryloyldimethyltaurate; ammonium sulfate; amylopectin; apricotamide DEA;apricotamidopropyl betaine; arachidyl alcohol; arachidyl glycol; arachishypogaea (peanut) flour; ascorbyl methylsilanol pectinate; astragalusgummifer gum; attapulgite; avena sativa (oat) kernel flour; avocadamideDEA; avocadamidopropyl betaine; azelamide MEA; babassuamide DEA;babassuamide MEA; babassuamidopropyl betaine; behenamide DEA; behenamideMEA; behenamidopropyl betaine; behenyl betaine; bentonite; butoxychitosan; caesalpinia spinosa gum; calcium alginate; calciumcarboxymethyl cellulose; calcium carrageenan; calcium chloride; calciumpotassium carbomer; calcium starch octenylsuccinate; C20-40 alkylstearate; canolamidopropyl betaine; capramide DEA;capryl/capramidopropyl betaine; carbomer; carboxybutyl chitosan;carboxymethyl cellulose acetate butyrate; carboxymethyl chitin;carboxymethyl chitosan; carboxymethyl dextran; carboxymethylhydroxyethylcellulose; carboxymethyl hydroxypropyl guar; carnitine;cellulose acetate propionate carboxylate; cellulose gum; ceratoniasiliqua gum; cetearyl alcohol; cetyl alcohol; cetyl babassuate; cetylbetaine; cetyl glycol; cetyl hydroxyethylcellulose; chimyl alcohol;cholesterol/HDI/pullulan copolymer; cholesteryl hexyl dicarbamatepullulan; citrus aurantium dulcis (orange) peel extract; cocamide DEA;cocamide MEA; cocamide MIPA; cocamidoethyl betaine; cocamidopropylbetaine; cocamidopropyl hydroxysultaine; coco-betaine;coco-hydroxysultaine; coconut alcohol; coco/oleamidopropyl betaine;coco-Sultaine; cocoyl sarcosinamide DEA; cornamide/cocamide DEA;cornamide DEA; croscarmellose; crosslinked bacillus/glucose/sodiumglutamate ferment; cyamopsis tetragonoloba (guar) gum; decyl alcohol;decyl betaine; dehydroxanthan gum; dextrin; dibenzylidene sorbitol;diethanolaminooleamide DEA; diglycol/CHDM/isophthalates/SIP copolymer;dihydroabietyl behenate; dihydrogenated tallow benzylmonium hectorite;dihydroxyaluminum aminoacetate; dimethicone/PEG-10 crosspolymer;dimethicone/PEG-15 crosspolymer; dimethicone propyl PG-betaine;dimethylacrylamide/acrylic acid/polystyrene ethyl methacrylatecopolymer; dimethylacrylamide/sodium acryloyldimethyltauratecrosspolymer; disteareth-100 IPDI; DMAPA acrylates/acrylicacid/acrylonitrogens copolymer; erucamidopropyl hydroxysultaine;ethylene/sodium acrylate copolymer; gelatin; gellan gum; glycerylalginate; glycine soja (soybean) flour; guar hydroxypropyltrimoniumchloride; hectorite; hyaluronic acid; hydrated silica; hydrogenatedpotato starch; hydrogenated tallow; hydrogenated tallowamide DEA;hydrogenated tallow betaine; hydroxybutyl methylcellulose; hydroxyethylacrylate/sodium acryloyldimethyl taurate copolymer;hydroxyethylcellulose; hydroxyethyl chitosan; hydroxyethylethylcellulose; hydroxyethyl stearamide-MIPA;hydroxylauryl/hydroxymyristyl betaine; hydroxypropylcellulose;hydroxypropyl chitosan; hydroxypropyl ethylenediamine carbomer;hydroxypropyl guar; hydroxypropyl methylcellulose; hydroxypropylmethylcellulose stearoxy ether; hydroxypropyl starch; hydroxypropylstarch phosphate; hydroxypropyl xanthan gum; hydroxystearamide MEA;isobutylene/sodium maleate copolymer; isostearamide DEA; isostearamideMEA; isostearamide mIPA; isostearamidopropyl betaine; lactamide MEA;lanolinamide DEA; lauramide DEA; lauramide MEA; lauramide MIPA;lauramide/myristamide DEA; lauramidopropyl betaine; lauramidopropylhydroxysultaine; laurimino bispropanediol; lauryl alcohol; laurylbetaine; lauryl hydroxysultaine; lauryl/myristyl glycol hydroxypropylether; lauryl sultaine; lecithinamide DEA; linoleamide DEA; linoleamideMEA; linoleamide MIPA; lithium magnesium silicate; lithium magnesiumsodium silicate; macrocystis pyrifera (kelp); magnesium alginate;magnesium/aluminum/hydroxide/carbonate; magnesium aluminum silicate;magnesium silicate; magnesium trisilicate; methoxy PEG-22/dodecyl glycolcopolymer; methylcellulose; methyl ethylcellulose; methylhydroxyethylcellulose; microcrystalline cellulose; milkamidopropylbetaine; minkamide DEA; minkamidopropyl betaine; MIPA-myristate;montmorillonite; Moroccan lava clay; myristamide DEA; myristamide MEA;myristamide MIPA; myristamidopropyl betaine; myristamidopropylhydroxysultaine; myristyl alcohol; myristyl betaine; natto gum;nonoxynyl hydroxyethylcellulose; oatamide MEA; oatamidopropyl betaine;octacosanyl glycol isostearate; octadecene/MA copolymer; oleamide DEA;oleamide MEA; oleamide MIPA; oleamidopropyl betaine; oleamidopropylhydroxysultaine; oleyl betaine; olivamide DEA; olivamidopropyl betaine;oliveamide MEA; palmamide DEA; palmamide MEA; palmamide MIPA;palmamidopropyl betaine; palmitamide DEA; palmitamide MEA;palmitamidopropyl betaine; palm kernel alcohol; palm kernelamide DEA;palm kernelamide MEA; palm kernelamide MIPA; palm kernelamidopropylbetaine; peanutamide MEA; peanutamide MIPA; pectin; PEG-800;PEG-crosspolymer; PEG-150/decyl alcohol/SMDI copolymer; PEG-175diisostearate; PEG-190 distearate; PEG-15 glyceryl tristearate; PEG-140glyceryl tristearate; PEG-240/HDI copolymer bis-decyltetradeceth-20ether; PEG-100/IPDI copolymer; PEG-180/laureth-50/™ MG copolymer;PEG-10/lauryl dimethicone crosspolymer; PEG-15/lauryl dimethiconecrosspolymer; PEG-2M; PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M;PEG-25M; PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M;PEG-120 methyl glucose trioleate; PEG-180/octoxynol-40/™ MG copolymer;PEG-150 pentaerythrityl tetrastearate; PEG-4 rapeseedamide;PEG-150/stearyl alcohol/SMDI copolymer; phaseolus angularis seed powder;polianthes tuberosa extract; polyacrylate-3; polyacrylic acid;polycyclopentadiene; polyether-1; polyethylene/isopropyl maleate/MAcopolyol; polyglyceryl-3 disiloxane dimethicone; polyglyceryl-3polydimethylsiloxyethyl dimethicone; polymethacrylic acid;polyquaternium-52; polyvinyl alcohol; potassium alginate; potassiumaluminum polyacrylate; potassium carbomer; potassium carrageenan;potassium chloride; potassium palmate; potassium polyacrylate; potassiumsulfate; potato starch modified; PPG-2 cocamide; PPG-1 hydroxyethylcaprylamide; PPG-2 hydroxyethyl cocamide; PPG-2 hydroxyethylcoco/isostearamide; PPG-3 hydroxyethyl soyamide; PPG-14 laureth-60 hexyldicarbamate; PPG-14 laureth-60 isophoryl dicarbamate; PPG-14 palmeth-60hexyl dicarbamate; propylene glycol alginate; PVP/decene copolymer; PVPmontmorillonite; pyrus cydonia seed; pyrus malus (apple) fiber;rhizobian gum; ricebranamide DEA; ricinoleamide DEA; ricinoleamide MEA;ricinoleamide MIPA; ricinoleamidopropyl betaine; ricinoleic acid/adipicacid/AEEA copolymer; rosa multiflora flower wax; sclerotium gum;sesamide DEA; sesamidopropyl betaine; sodium acrylate/acryloyldimethyltaurate copolymer; sodium acrylates/acrolein copolymer; sodiumacrylates/acrylonitrogens copolymer; sodium acrylates copolymer; sodiumacrylates crosspolymer; sodium acrylate/sodium acrylamidomethylpropanesulfonate copolymer; sodium acrylates/vinyl isodecanoate crosspolymer;sodium acrylate/vinyl alcohol copolymer; sodium carbomer; sodiumcarboxymethyl chitin; sodium carboxymethyl dextran; sodium carboxymethylbeta-glucan; sodium carboxymethyl starch; sodium carrageenan; sodiumcellulose sulfate; sodium chloride; sodium cyclodextrin sulfate; sodiumhydroxypropyl starch phosphate; sodium isooctylene/MA copolymer; sodiummagnesium fluorosilicate; sodium oleate; sodium palmitate; sodium palmkernelate; sodium polyacrylate; sodium polyacrylate starch; sodiumpolyacryloyldimethyl taurate; sodium polygamma-glutamate; sodiumpolymethacrylate; sodium polystyrene sulfonate; sodium silicoaluminate;sodium starch octenylsuccinate; sodium stearate; sodium stearoxyPG-hydroxyethylcellulose sulfonate; sodium styrene/acrylates copolymer;sodium sulfate; sodium tallowate; sodium tauride acrylates/acrylicacid/acrylonitrogens copolymer; sodium tocopheryl phosphate; solanumtuberosum (potato) starch; soyamide DEA; soyamidopropyl betaine;starch/acrylates/acrylamide copolymer; starch hydroxypropyltrimoniumchloride; stearamide AMP; stearamide DEA; stearamide DEA-distearate;stearamide DIBA-stearate; stearamide MEA; stearamide MEA-stearate;stearamide MIPA; stearamidopropyl betaine; steareth-60 cetyl ether;steareth-100/PEG-136/HDI copolymer; stearyl alcohol; stearyl betaine;sterculia urens gum; synthetic fluorphlogopite; tallamide DEA; tallowalcohol; tallowamide DEA; tallowamide MEA; tallowamidopropyl betaine;tallowamidopropyl hydroxysultaine; tallowamine oxide; tallow betaine;tallow dihydroxyethyl betaine; tamarindus indica seed gum; tapiocastarch; TEA-alginate; TEA-carbomer; TEA-hydrochloride; trideceth-2carboxamide MEA; tridecyl alcohol; triethylene glycol dibenzoate;trimethyl pentanol hydroxyethyl ether; triticum vulgare (wheat) germpowder; triticum vulgare (wheat) kernel flour; triticum vulgare (wheat)starch; tromethamine acrylates/acrylonitrogens copolymer; tromethaminemagnesium aluminum silicate; undecyl alcohol; undecylenamide DEA;undecylenamide MEA; undecylenamidopropyl betaine; welan gum; wheatgermamide DEA; wheat germamidopropyl betaine; xanthan gum; yeastbeta-glucan; yeast polysaccharides; zea mays (corn) starch; and blendsthereof.

Also suitable as thickeners and/or viscosifiers are the followingcommercial products:

(1) Aqualon™ carboxymethylcellulose, Benecel™ methylcellulose andhydroxypropyl methylcellulose, Blanose™ sodium carboxymethylcellulose,Klucel™ hydroxypropylcellulose, Natrosol™ hydroxyethylcellulose,Natrosol™ Plus and PolySurf™ cetyl modified hydroxyethylcellulose,n-Hance™ cationic guar, n-Hance™ HP Series hydroxypropyl guar, n-Hance™SP-100 conditioning polymer, and Supercol™ guar gum from AshlandSpecialty Ingredients

(2) Carbopol® Polymers, Fixate™ PLUS Polymer, Glucamate™ Thickeners,Amidex™ Surfactants, Chembetaine™ Surfactants, Chemoxide™ Surfactants,Chemonic™ Surfactants, Chemccinate™ Surfactants, Amidex™ BC-24Surfactant, Chemoryl™ LB-30 Surfactant, Novethix™ L-10 Polymer, Ceralan™Lanolin Product, Pemulen™ TR-1 Polymeric Emulsifier, Pemulen™ TR-2Polymeric Emulsifier, Hydramol™ PGPD Ester, Schercodine™ M Amido-Amine,Schercodine™ P Amido-Amine, Schercomid™ Diethanolamides from TheLubrizol Corporation.

(3) Salcare® and Luvigel® from BASF Corporation.

(4) Aculyn™ 22, Aculyn™ 28, Aculyn™ 33, Aculyn™ 38, and Aculyn™ 44 fromThe Dow Chemical Company.

(5) Ammonyx® C and Stepan-Mild® GCC from Stepan Company.

(6) Stabileze™, Rapithix™ A-60, Rapithix™ A-100, Ultrathix™ P-100,Lubrajel™ and FlexiThix™ from Ashland Specialty Ingredients (Wayne,N.J.).

Also suitable as a thickener/rheology modifier are lightly- tomoderately-crosslinked polyvinylpyrrolidones. Disclosures of thesepolymers are provided in the following publications, each of which ishereby incorporated in its entirety by reference: U.S. Pat. Nos.5,073,614; 5,312,619; 5,139,770; 5,716,634; 5,470,884; 5,759,524;5,997,887; 6,024,942; as well as international application PCT/US10/26973, PCT/US 10/26976, PCT/US 10/26940, PCT/US 11/32993, and PCT/US11/34515.

Personal care compositions may comprise natural extracts and/or naturalproducts. Extensive details on natural products that can be used inpersonal care compositions is provided in book chapter “Chemistry ofCosmetics, Comprehensive Natural Products II” in Chemistry and Biology;volume 3, 2010.

Oral Care Composition Ingredients

Non-limiting applications of the oral care compositions include: toothand/or mouth cleansing, providing denture adhesion, delivering and/orretaining actives to oral cavity, mouth washing, mouth refreshing, mouthrinsing, mouth gargling, providing oral hygiene, preventing, reducing,controlling, and/or removing tooth stain, preventing and/or controllingtooth decay, preventing and/or controlling tartar, tooth flossing, toothwhitening and/or bleaching, mouth treating, and tooth filling.

Oral care compositions may optionally contain one or more additionalingredients. Non-limiting examples of suitable ingredients include:carriers, dentifrices, cleaning agents, breath freshening actives, painrelievers, anesthetics, anti-inflammatory agents, antimicrobial agents,antibacterial agents, anti-calculus agents, anti-plaque agents, gums,thickeners, gelling agents, surfactants, flavors, warming or tinglingagents, tooth bleaching agents, whiteners, stain removers, stainpreventers, abrasives, adhesives, colors, emollients, emulsifiers,preservatives, solvents, binders, stimulants, depressants, diet aids,smoking cessation aides, vitamins, minerals, throat-soothing agents,spices, herbs, herbal extracts, alkaloids (such as caffeine andnicotine), and humectants.

The choice of a carrier to be used is basically determined by the waythe composition is to be introduced into the oral cavity. Carriermaterials for toothpaste, tooth gel or the like include abrasivematerials, sudsing agents, binders, humectants, flavoring and sweeteningagents, as disclosed in e.g., U.S. Pat. No. 3,988,433. Carrier materialsfor biphasic dentifrice compositions are disclosed in U.S. Pat. Nos.5,213,790; 5,145,666; 5,281,410; 4,849,213; and 4,528,180. Mouthwash,rinse or mouth spray carrier materials typically include water,flavoring and sweetening agents, etc., as disclosed in, e.g., U.S. Pat.No. 3,988,433. Lozenge carrier materials typically include a candy base;chewing gum carrier materials include a gum base, flavoring andsweetening agents, as in, e.g., U.S. Pat. No. 4,083,955. Sachet carriermaterials typically include a sachet bag, flavoring and sweeteningagents. For sub-gingival gels used for delivery of actives into theperiodontal pockets or around the periodontal pockets, a “sub-gingivalgel carrier” is chosen as disclosed in, e.g., U.S. Pat. Nos. 5,198,220and 5,242,910. The selection of a carrier will depend on secondaryconsiderations like taste, cost, and shelf stability, and other factors.

Oral care compositions may comprise one or more dental abrasives. Dentalabrasives useful in the compositions include many different materials.The material selected must be one which is compatible within thecomposition of interest and does not excessively abrade dentin.

Non-limiting examples of suitable abrasives include: silicas includinggels and precipitates, insoluble sodium polymetaphosphate, hydratedalumina, calcium carbonate, dicalcium orthophosphate dihydrate, calciumpyrophosphate, tricalcium phosphate, calcium polymetaphosphate, resinousabrasive materials such as particulate condensation products of urea andformaldehyde, and blends thereof.

Another class of abrasives is the particulate thermo-setting polymerizedresins as described in U.S. Pat. No. 3,070,510.

Non-limiting examples of suitable resins include: melamines, phenolics,ureas, melamine-ureas, melamine-formaldehydes, urea-formaldehyde,melamine-urea-formaldehydes, cross-linked epoxides, cross-linkedpolyesters, and blends thereof.

Silica dental abrasives of various types may be employed because oftheir unique benefits of exceptional dental cleaning and polishingperformance without unduly abrading tooth enamel or dentine. The silicaabrasive polishing materials herein, as well as other abrasives,generally have an average particle size ranging from about 0.1 to about30 microns, and particularly from about 5 to about 15 microns. Theabrasive can be precipitated silica or silica gels such as the silicaxerogels described in U.S. Pat. No. 3,538,230, and U.S. Pat. No.3,862,307.

Non-limiting examples of suitable silica abrasives include: silicaxerogels marketed under the trade name “Syloid” by the W.R. Grace &Company, Davison Chemical Division and precipitated silica materialssuch as those marketed by the J.M. Huber Corporation under the tradename, Zeodent®, particularly the silicas carrying the designationZeodent® 119, Zeodent® 118, Zeodent® 109 and Zeodent® 129. The types ofsilica dental abrasives useful in the toothpastes of the invention aredescribed in more detail in U.S. Pat. Nos. 4,340,583; 5,603,920;5,589,160; 5,658,553; 5,651,958; and 6,740,311. Each of thesedisclosures is hereby incorporated in its entirety by reference.

Mixtures of abrasives can be used such as mixtures of the various gradesof Zeodent® silica abrasives listed above.

The total amount of abrasive(s) in the oral care compositions typicallyrange from about 6% to about 70% by weight; toothpastes may contain fromabout 10% to about 50% of abrasives by weight of the composition. Dentalsolution, mouth spray, mouthwash and non-abrasive gel compositionstypically contain little or no abrasives.

Oral care compositions may comprise polymeric mineral surface activeagent(s) (PMSAs). PMSAs include any agent which will have a strongaffinity for the tooth surface, deposit a polymer layer or coating onthe tooth surface and produce the desired surface modification effects.The “mineral” descriptor is intended to convey that the surface activityor substantivity of the polymer is toward mineral surfaces such ascalcium phosphate minerals or teeth.

Non-limiting examples of suitable PMSAs include: polyelectrolytes suchas condensed phosphorylated polymers; polyphosphonates; copolymers ofphosphate- or phosphonate-containing monomers or polymers with othermonomers such as ethylenically unsaturated monomers and amino acids orwith other polymers such as proteins, polypeptides, polysaccharides,poly(acrylate), poly(acrylamide), poly(methacrylate), poly(ethacrylate),poly(hydroxyalkylmethacrylate), poly(vinyl alcohol), poly(maleicanhydride), poly(maleate) poly(amide), poly(ethylene amine),poly(ethylene glycol), poly(propylene glycol), poly(vinyl acetate),poly(vinyl benzyl chloride), polycarboxylates, carboxy-substitutedpolymers, and blends thereof. Also suitable as polymeric mineral surfaceactive agents are the carboxy-substituted alcohol polymers described inU.S. Pat. Nos. 5,292,501; 5,213,789, 5,093,170; 5,009,882; and4,939,284; and the diphosphonate-derivatized polymers in U.S. Pat. No.5,011,913; the synthetic anionic polymers including polyacrylates andcopolymers of maleic anhydride or acid and methyl vinyl ether (e.g.,Gantrez®), as described, for example, in U.S. Pat. No. 4,627,977.Another example of a polymeric mineral surface active agent is adiphosphonate modified polyacrylic acid.

Polymers with activity must have sufficient surface binding propensityto desorb pellicle proteins and remain affixed to enamel surfaces. Fortooth surfaces, polymers with end or side chain phosphate or phosphonatefunctions may be used, although other polymers with mineral bindingactivity may prove effective depending upon adsorption affinity.

PMSAs are useful in the compositions because of their stain preventionbenefit. It is believed the PMSAs provide a stain prevention benefitbecause of their reactivity or substantivity to mineral surfaces,resulting in desorption of portions of undesirable adsorbed pellicleproteins, in particular those associated with binding color bodies thatstain teeth, calculus development and attraction of undesirablemicrobial species. The retention of these PMSAs on teeth can alsoprevent stains from accruing due to disruption of binding sites of colorbodies on tooth surfaces.

The ability of PMSA to bind stain promoting ingredients of oral careproducts such as stannous ions and cationic antimicrobials is alsobelieved to be helpful. The PMSA will also provide tooth surfaceconditioning effects which produce desirable effects on surfacethermodynamic properties and surface film properties, which impartimproved clean feel aesthetics both during and most importantly,following rinsing or brushing. Many of these polymeric agents are alsoknown or expected to provide tartar control benefits when applied inoral compositions, hence providing improvement in both the appearance ofteeth and their tactile impression to consumers. The desired surfaceeffects may include: 1) creating a hydrophilic tooth surface immediatelyafter treatment; and 2) maintaining surface conditioning effects andcontrol of pellicle film for extended periods following product use,including post brushing or rinsing and throughout more extended periods.The effect of creating an increased hydrophilic surface can be measuredin terms of a relative decrease in water contact angles. The hydrophilicsurface, importantly, is maintained on the tooth surface for an extendedperiod after using the product.

Oral care compositions may comprise additional anticalculus agent(s),such as a pyrophosphate salt as a source of pyrophosphate ion.

Non-limiting examples of suitable pyrophosphate salts include: dialkalimetal pyrophosphate salts, tetraalkali metal pyrophosphate salts, andmixtures thereof. Particularly, disodium dihydrogen pyrophosphate(Na₂H₂P₂O₇), tetrasodium pyrophosphate (Na₄P₂O₇), and tetrapotassiumpyrophosphate (K₄P₂O₇) in their unhydrated as well as hydrated forms mayfind utility.

In compositions of the invention, the pyrophosphate salt may be presentin one of three ways: predominately dissolved, predominatelyundissolved, or a mixture of dissolved and undissolved pyrophosphate.

Compositions comprising predominately dissolved pyrophosphate refer tocompositions where at least one pyrophosphate ion source is in an amountsufficient to provide at least about 1.0% free pyrophosphate ions. Theamount of free pyrophosphate ions may be from about 1% to about 15%,particularly from about 1.5% to about 10%, and more particularly fromabout 2% to about 6%. Free pyrophosphate ions may be present in avariety of protonated states depending on the pH of the composition.

Compositions comprising predominately undissolved pyrophosphate refer tocompositions containing no more than about 20% of the totalpyrophosphate salt dissolved in the composition, particularly less thanabout 10% of the total pyrophosphate dissolved in the composition.Tetrasodium pyrophosphate salt may be one such pyrophosphate salt inthese compositions. Tetrasodium pyrophosphate may be the anhydrous saltform or the decahydrate form, or any other species stable in solid formin the oral care compositions. The salt is in its solid particle form,which may be its crystalline and/or amorphous state, with the particlesize of the salt being small enough to be aesthetically acceptable andreadily soluble during use. The amount of pyrophosphate salt useful inmaking these compositions is any tartar control effective amount,generally from about 1.5% to about 15%, particularly from about 2% toabout 10%, and more particularly from about 3% to about 8% by weight ofthe oral care composition.

The pyrophosphate salts are described in more detail in Kirk-OthmerEncyclopedia of Chemical Technology, third edition, volume 17,Wiley-Interscience Publishers (1982).

Oral care compositions may comprise peroxide compounds.

Non-limiting examples of suitable peroxide compounds include: hydrogenperoxide and organic peroxides including urea peroxide, carbamideperoxide, glyceryl peroxide, benzoyl peroxide, derivatives thereof, andblends thereof.

Typically, the peroxide compound can be employed in amounts so that atleast about 1% by weight of the composition comprises peroxide. Theperoxide compound may comprise from about 2% to about 30% by weight ofthe composition. More particularly, the peroxide comprises from about 3%to about 15% by weight of the composition. A typical peroxideconcentration in the composition is generally from about 2% to about 7%by weight for home use products, and from about 15% to about 20% byweight for dental professional use.

Thickening or gelling agents used in dentifrice compositions may includenonionic polyoxyethylene polyoxypropylene block copolymers. Illustrativeof polyoxyethylene polyoxypropylene block copolymers useful in thepractice include block copolymers having the formulaHO(C₂H₄O)_(b)(C₃H₆O₆)_(a)(C₂H₄O)_(b)H wherein a is an integer such thatthe hydrophobic base represented by (C₃H₆O₆) has a molecular weight ofabout 2,750 Da to 4000 Da, b is an integer such that the hydrophilicportion (moiety) represented by (C₂H₄O) constitutes from about 70% toabout 80% by weight of the copolymer. Block copolymers of thiscomposition are available commercially under the trademark Pluronic® Ftype.

Pluronic® F127 has a molecular weight of 4,000 Da and contains 70% ofthe hydrophilic polyoxyethylene moiety.

Also suitable as a thickening agent is lightly- tomoderately-crosslinked PVP, described in international applicationPCT/US 11/30642.

The thickening agents may be present in an amount from about 15% toabout 50% by weight, particularly from about 25% to about 45% by weightof the composition.

Surfactants may also be included in the oral care compositions of theinvention, where they may serve in solubilizing, dispersing, emulsifyingand/or reducing the surface tension of the teeth in order to increasethe contact between the tooth and the peroxide. The compositions mayalso comprise surfactants, also commonly referred to as sudsing agents.Suitable surfactants are those which are reasonably stable and foamthroughout a wide pH range. Surfactants may be chosen from anionic,nonionic, amphoteric, zwitterionic, or cationic surfactants, or blendsthereof.

Anionic surfactants useful herein include the water-soluble salts ofalkyl sulfates having from 8 to 20 carbon atoms in the alkyl radical(e.g., sodium alkyl sulfate) and the water-soluble salts of sulfonatedmonoglycerides of fatty acids having from 8 to 20 carbon atoms. Sodiumlauryl sulfate (SLS) and sodium coconut monoglyceride sulfonates arenon-limiting examples of anionic surfactants of this type. Many suitableanionic surfactants are disclosed in U.S. Pat. No. 3,959,458. Thecompositions may comprise an anionic surfactant in an amount from about0.025% to about 9% by weight, particularly from about 0.05% to about 5%by weight, and more particularly from about 0.1% to about 1% by weightof the composition.

Non-limiting examples of suitable anionic surfactants include:sarcosinates, taurates, isethionates, sodium lauryl sulfoacetate, sodiumlaureth carboxylate, and sodium dodecyl benzenesulfonate. Also suitableare alkali metal or ammonium salts of surfactants such as the sodium andpotassium salts of the following: lauroyl sarcosinate, myristoylsarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate, and oleoylsarcosinate. The sarcosinate surfactant may be present in thecompositions from about 0.1% to about 2.5%, particularly from about 0.5%to about 2.0% by weight of the total composition.

Non-limiting examples of suitable cationic surfactants include:derivatives of aliphatic quaternary ammonium compounds having at leastone long alkyl chain containing from about 8 to about 18 carbon atomssuch as lauryl trimethylammonium chloride, cetyl pyridinium chloride,cetyl trimethylammonium bromide,di-isobutylphenoxyethyl-dimethylbenzylammonium chloride, coconutalkyltrimethylammonium nitrite, cetyl pyridinium fluoride, and blendsthereof. Also suitable are the quaternary ammonium fluorides describedin U.S. Pat. No. 3,535,421, where the quaternary ammonium fluorides havedetergent properties. Certain cationic surfactants can also act asgermicides in the compositions disclosed herein.

Nonionic surfactants that may be used in the compositions of theinvention include compounds produced by the condensation of alkyleneoxide groups (hydrophilic in nature) with an organic hydrophobiccompound which may be aliphatic or alkylaromatic in nature.

Non-limiting examples of suitable nonionic surfactants include:poloxamers (sold under the trade name Pluronic® by BASF Corporation),polyethylene oxide condensates of alkyl phenols, products derived fromthe condensation of ethylene oxide with the reaction product ofpropylene oxide and ethylene diamine, ethylene oxide condensates ofaliphatic alcohols, long chain tertiary amine oxides, long chaintertiary phosphine oxides, long chain dialkyl sulfoxides and blendsthereof.

Non-limiting examples of suitable zwitterionic surfactants includebetaines and derivatives of aliphatic quaternary ammonium compounds inwhich the aliphatic radicals can be straight chain or branched, andwhich contain an anionic water-solubilizing group, e.g., carboxy,sulfonate, sulfate, phosphate, or phosphonate.

Non-limiting examples of suitable betaines include: decyl betaine or2-(N-decyl-N,N-dimethylammonio)acetate, coco betaine or2-(N-coc-N,N-dimethyl ammonio)acetate, myristyl betaine, palmitylbetaine, lauryl betaine, cetyl betaine, stearyl betaine, and blendsthereof. The amidobetaines are exemplified by cocoamidoethyl betaine,cocoamidopropyl betaine, lauramidopropyl betaine, and the like. Thebetaines of choice include cocoamidopropyl betaines such aslauramidopropyl betaine. Suitable betaine surfactants are disclosed inU.S. Pat. No. 5,180,577.

Other surfactants such as fluorinated surfactants may also beincorporated within the compositions of the invention.

Oral care compositions may comprise flavor(s).

Non-limiting examples of suitable flavors include: methyl salicylate,ethyl salicylate, methyl cinnamate, ethyl cinnamate, butyl cinnamate,ethyl butyrate, ethyl acetate, methyl anthranilate, iso-amyl acetate,iso-armyl butyrate, allyl caproate, eugenol, eucalyptol, thymol,cinnamic alcohol, cinnamic aldehyde, octanol, octanal, decanol, decanal,phenylethyl alcohol, benzyl alcohol, benzaldehyde, α-terpineol,linalool, limonene, citral, vanillin, ethyl vanillin, propenyl guaethol,maltol, ethyl maltol, heliotropin, anethole, dihydroanethole, carvone,oxanone, menthone, β-damascenone, ionone, gamma decalactone, gammanonalactone, gamma undecalactone, 4-hydroxy-2,5-dimethyl-3(2H)-furanone,and blends thereof.

Generally suitable flavoring agents are those containing structuralfeatures and functional groups that are less prone to oxidation byperoxide. These include derivatives of flavor chemicals that aresaturated or contain stable aromatic rings or ester groups.

Also suitable are flavor chemicals that may undergo some oxidation ordegradation without resulting in a significant change in the flavorcharacter or profile. The flavor chemicals, including menthol, may beprovided as single or purified chemicals rather than supplied in thecomposition by addition of natural oils or extracts such as peppermint,spearmint, or wintergreen oils as these sources may contain othercomponents that are relatively unstable and may degrade in the presenceof peroxide. Flavoring agents are generally used in the compositions atlevels of from about 0.001% to about 5% by weight of the composition.

The flavor system may typically include sweetening agent(s). Sweetenersinclude compounds of natural and artificial origin.

Non-limiting examples of suitable water-soluble natural sweetenersinclude: monosaccharides, disaccharides and polysaccharides, such asxylose, ribose, glucose (dextrose), mannose, galactose, fructose(levulose), sucrose (sugar), maltose, invert sugar (a mixture offructose and glucose derived from sucrose), partially hydrolyzed starch,corn syrup solids, dihydrochalcones, monellin, steviosides,glycyrrhizin, and blends thereof.

Non-limiting examples of suitable water-soluble artificial sweetenersinclude: soluble saccharin salts, i.e., sodium or calcium saccharinsalts, cyclamate salts, the sodium, ammonium or calcium salt of3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide, the potassiumsalt of 3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide(acesulfame-K), the free acid form of saccharin, and the like. Othersuitable sweeteners include dipeptide based sweeteners, such asL-aspartic acid derived sweeteners, such as L-aspartyl-L-phenylalaninemethyl ester (aspartame) and materials described in U.S. Pat. No.3,492,131,L-α-aspartyl-N-(2,2,4,4-tetramethyl-3-thietanyl)-D-alaninamide hydrate,methyl esters of L-aspartyl-L-phenylglycerin and L-aspartyl-L-2,5,dihydrophenyl-glycine, L-aspartyl-2,5-dihydro-L-phenylalanine,L-aspartyl-L-(1-cyclohexyen)-alanine, derivatives thereof, and blendsthereof. Water-soluble sweeteners derived from naturally occurringwater-soluble sweeteners, such as a chlorinated derivative of ordinarysugar (sucrose), known, for example, under the product description ofsucralose as well as protein based sweeteners such as thaumatoccousdanielli (Thaumatin I and II) may be used. The compositions may containsweetener(s) in an amount from about 0.1% to about 10% by weight, inparticular from about 0.1% to about 1% by weight of the composition.

In addition, the flavor system may include salivating agents, warmingagents, and numbing agents. These agents are present in the compositionsin an amount from about 0.001% to about 10% by weight, particularly fromabout 0.1% to about 1% by weight of the composition.

A non-limiting example of suitable salivating agent includes Jambus®manufactured by Takasago. Non-limiting examples of suitable warmingagents include capsicum and nicotinate esters such as benzyl nicotinate.Non-limiting examples of suitable numbing agents include benzocaine,lidocaine, clove bud oil, ethanol, and blends thereof.

Oral care compositions may comprise chelating agent(s).

The chelating agents may include metal solubilizing agents and metalprecipitating agents. The metal solubilizing agents include a condensedpyrophosphate compound. For purposes of this invention “condensedphosphate” relates to an inorganic phosphate composition containing twoor more phosphate species in a linear or cyclic pyrophosphate form. Thecondensed phosphate may be sodium pyrophosphate, but may also includetripolyphosphate, hexametaphosphate, cyclic condensed phosphate or othersimilar phosphates well known in the field. The blend may also includean organic chelating agent. The term “organic phosphate” includesphosphonic acid, di and tri phosphonoc acid compound or its salts. Anexample of phosphonic acid is 1-hydroxyethylidene-1,1-diphosphonic acidthat is sold under the trade name of Dequest®. The blend may alsoinclude a metal precipitating chelating agent. The term “metalprecipitating chelating agent” is an agent that binds to metals andcauses the metal to precipitate and includes halogens such as fluoride.The chelating agents are incorporated in the oral care compositions ofthe invention in an amount from about 0.1% to about 8.0% by weight, andparticularly from about 0.5% to about 3.0% by weight of the composition,in a ratio of about 3:1:1 w/w organic chelating agent: condensedphosphate chelating agent: metal precipitating agent.

Another optional ingredient that may be used in oral care compositionsis a humectant. For example, a humectant may be added to keep toothpastecompositions from hardening upon exposure to air, to give compositions amoist feel to the mouth, and, for particular humectants, to impartdesirable sweetness of flavor to toothpaste compositions. The humectant,on a pure humectant basis, is generally present from about 0% to about70%, particularly from about 5% to about 25% by weight of thecomposition.

Non-limiting examples of suitable humectants include: edible polyhydricalcohols such as glycerin, sorbitol, xylitol, butylene glycol,polyethylene glycol, propylene glycol, trimethyl glycine, and blendsthereof.

The invention also contemplates oral care compositions comprisingpolymer(s) described herein complexed with hydrogen peroxide. Adescription of such complexes is present in international application WO91/07184, the contents of which are hereby incorporated in theirentirety by reference.

Also contemplated are oral care compositions such as those described inthe following patents and patent applications, the contents of each arehereby incorporated in their entirety by reference: WO 2011/068514, WO2011/053877, US 2010/0275394, US 2011/0076090, US 2008/091935, US2008/0181716, US 2008/0014224, WO 2007/066837, US 2008/0292669, US2007/0071696, US 2007/0154863, US 2008/0317797, US 2005/0249678, US2007/0178055, US 2007/0189983, WO 2005/041910, U.S. Pat. No. 7,785,572,WO 1998/005749, WO 1997/022651, and U.S. Pat. No. 5,310,563.

Oral care compositions may comprise one or more denture adhesives.

Synthetic materials presently dominate the denture adhesive market. Suchmaterials may consist of mixtures of the salts of short-acting polymers(e.g., carboxymethylcellulose or “CMC”) and long-acting polymers (e.g.,poly[vinyl methyl ether maleate], or “Gantrez” and its salts).Polyvinylpyrrolidone (povidone) may also be used.

Other components of denture adhesive products impart particular physicalattributes to the compositions. Petrolatum, mineral oil, andpolyethylene oxide may be included in creams to bind the materials andto make their placement easier. Silicon dioxide and calcium stearate maybe used in powders to minimize clumping. Menthol and peppermint oils maybe used for flavoring, red dye for color, and sodium borate and methyl-or poly-paraben as preservatives.

It is also contemplated that the composition ingredients may beformulated in a single container, or the ingredients may be formulatedin-part in two or more distinct containers of the same or differenttype, the contents of which may require mixing prior to use.

Particular, yet non-limiting examples of properties that can bebeneficially modified by the polymers and polymer compositions disclosedherein are solution viscosity, rheology, thickening, film formation,lubricity, gloss, adhesion, impact resistance, fluid snap, filmbrittleness, film toughness, coating hardness, water resistance, tack,surface gloss and shine, surface tension, wetting, foaming and foamstabilization, tensile strength, solvency, solubilization speed,compatibility, bio-adhesion, particulate suspension, particulatedispersive properties, dispersive properties, delivery of hydrophobiccompositions, formulation stabilization, flexibility, chemicalresistance, abrasion resistance, penetration, and combinations thereof.

In particular embodiments, the polymers that are components of personalcare compositions according to the invention have the property ofmodifying the rheology of the compositions.

In a second aspect, the invention provides a method of providinghairstyle retention to hair at a relative humidity exceeding about 40%,the method comprising applying onto the hair a hair care compositioncomprising a polymer having the structure:

wherein each Q is a hydrocarbyl moiety comprising at least one hydroxyland optionally at least one ether; each R₁ is a functionalized orunfunctionalized alkyl; a is a value ranging from about 0.1 to 100percent by weight of the polymer; and each b and c is an independentlyselected value ranging from 0 to about 99.9 percent by weight of thepolymer, with the proviso that the sum of a, b and c for the polymerequals 100 weight percent.

In particular embodiments of the method of providing hairstyle retentionto hair at a relative humidity exceeding about 40% according to theinvention, the polymer in the hair care composition is present in anamount from about 0.1 percent by weight to about 10 percent by weight ofthe hair care composition. More particularly, the polymer is present inan amount from about 0.1 percent by weight to about 5.0 percent byweight of the hair care composition. Even more particularly, the polymeris present in an amount from about 0.1 percent by weight to about 2.5percent by weight of the hair care composition.

General Methods of Synthesis

Free radical polymerization may be used, especially when usingwater-dispersible and/or water-soluble reaction solvent(s). This type ofpolymerization method is described in “Decomposition Rate of OrganicFree Radical Polymerization” by K. W. Dixon (section II in PolymerHandbook, volume 1, 4th edition, Wiley-Interscience, 1999), which isherein incorporated in its entirety by reference.

Compounds capable of initiating the free-radical polymerization includethose materials known to function in the prescribed manner, and includethe peroxo and azo classes of materials. Peroxo and azo compoundsinclude, but are not limited to: acetyl peroxide; azobis-(2-amidinopropane) dihydrochloride; azo bis-isobutyronitrile;2,2′-azo bis-(2-methylbutyronitrile); benzoyl peroxide; di-tert-amylperoxide; di-tert-butyl diperphthalate; butyl peroctoate; tert-butyldicumyl peroxide; tert-butyl hydroperoxide; tert-butyl perbenzoate;tert-butyl permaleate; tert-butyl perisobutylrate; tert-butylperacetate; tert-butyl perpivalate; para-chlorobenzoyl peroxide; cumenehydroperoxide; diacetyl peroxide; dibenzoyl peroxide; dicumyl peroxide;didecanoyl peroxide; dilauroyl peroxide; diisopropyl peroxodicarbamate;dioctanoyl peroxide; lauroyl peroxide; octanoyl peroxide; succinylperoxide; and bis-(ortho-toluoyl) peroxide. Also suitable to initiatethe free-radical polymerization are initiator mixtures or redoxinitiator systems, including: ascorbic acid/iron (II) sulfate/sodiumperoxodisulfate, tert-butyl hydroperoxide/sodium disulfite, andtert-butyl hydroperoxide/sodium hydroxymethanesulfinate.

The polymerization reactions may be carried out in the presence of oneor more solvents. The polymers may be synthesized in a solvent or ablend of one or more solvents and maintained therein, or the synthesissolvent(s) separated from the polymer by methods known in the art andreplaced by a solvent beneficial for formulary development and/orend-use. The polymerization temperature may vary from about 5° C. toabout 200° C. The polymerization reaction may be carried out at ambientpressure, sub-atmospheric pressure, or super-atmospheric pressure. Thepolymerization reaction may be carried out in a batch, continuous and/orsemi-continuous manner.

In particular embodiments, the polymers that are components of personalcare compositions according to the invention may have a weight-averagemolecular weight ranging from about 5,000 Da to about 10,000,000 Da,more particularly from about 10,000 Da to about 1000,000 Da, and evenmore particularly from about 25,000 Da to about 500,000 Da.

The molecular weight of polymers may be controlled using methods knownin the art, including strategies to control the reaction temperature andtime, as well as the use of chain-transfer agents such as thiols (e.g.,dodecyl mercaptan), and halocarbons (e.g., chlorinated compounds likecarbon tetrachloride).

Characterization

The polymers and compositions comprising the polymers according to theinvention may be analyzed by known techniques. Especially preferred arethe techniques of ¹³C nuclear magnetic resonance (NMR) spectroscopy, gaschromatography (GC), and gel permeation chromatography (GPC) in order todecipher polymer identity, residual monomer concentrations, polymermolecular weight, and polymer molecular weight distribution.

Nuclear magnetic resonance (NMR) spectroscopy is an especially preferredmethod to probe the polymerization product in terms of chemicalproperties such as monomeric composition, sequencing and tacticity.Analytical equipment suitable for these analyses includes the Inova400-MR NMR System by Varian Inc. (Palo Alto, Calif.). References broadlydescribing NMR include: Yoder, C. H. and Schaeffer Jr., C. D.,Introduction to Multinuclear NMR, The Benjamin/Cummings PublishingCompany, Inc., 1987; and Silverstein, R. M., et al., SpectrometricIdentification of Organic Compounds, John Wiley & Sons, 1981, which areincorporated in their entirety by reference.

Residual monomer levels can be measured by GC, which can be used toindicate the extent of reactant conversion by the polymerizationprocess. GC analytical equipment to perform these tests are commerciallyavailable, and include the following units: Series 5880, 5890, and 6890GC-FID and GC-TCD by Agilent Technologies, Inc. (Santa Clara, Calif.).GC principles are described in Modern Practice of Gas Chromatography,third edition (John Wiley & Sons, 1995) by Robert L. Grob and Eugene F.Barry, which is herein incorporated in its entirety by reference.

GPC is an analytical method that separates molecules based on theirhydrodynamic volume (or size) in solution of the mobile phase, such ashydroalcoholic solutions with surfactants. GPC is a preferred method formeasuring polymer molecular weight distributions. This technique can beperformed on known analytical equipment sold for this purpose, andinclude the TDAmax™ Elevated Temperature GPC System and the RImax™Conventional Calibration System by Viscotek™ Corp. (Houston, Tex.). Inaddition, GPC employs analytical standards as a reference, of which aplurality of narrow-distribution polyethylene glycol and polyethyleneoxide standards representing a wide range in molecular weight is thepreferred. These analytical standards are available for purchase fromRohm & Haas Company (Philadelphia, Pa.) and Varian Inc. (Palo Alto,Calif.). GPC is described in the following texts, which are hereinincorporated in their entirety by reference: Schroder, E., et al.,Polymer Characterization, Hanser Publishers, 1989; Billingham, N.C.,Molar Mass Measurements in Polymer Science, Halsted Press, 1979; andBillmeyer, F., Textbook of Polymer Science, Wiley Interscience, 1984.

All references including patent applications and publications citedherein are incorporated herein by reference in their entirety and forall purpose to the same extent as if each individual publication orpatent or patent application was specifically and individually indicatedto be incorporated by reference in its entirety for all purposes. Manymodifications and variations of the presently disclosed and claimedinventive concept(s) can be made without departing from its spirit andscope, as will be apparent to those skilled in the art.

The compositions comprising the polymers according to the invention maybe prepared and tested according to the examples and test methods setout below. The examples and test methods are presented for purposes ofdemonstrating, but not limiting, the preparation and testing of thecompositions. Therein, the following abbreviations are used:

PVOH: Polyvinyl alcohol

Gly: Glycidol

PVOH-g-Gly: Polyvinyl alcohol-glycidol adduct polymer

RH: Relative Humidity

Examples of Synthesis of Polymers Example 1

Synthesis of Polyvinyl Alcohol-Glycidol Adduct Polymer

An amount of 20 g of high molecular weight PVOH (0.45 moles) wasdissolved in water (160 ml) at 100° C. To this, an amount of 4.6 ml of5.0 M aqueous NaOH was added. To this mixture, an amount of 60 mlglycidol (0.91 moles) was added. The reaction mixture was maintained at100° C. for 24 hours followed by neutralization with aqueous HCl toquench the reaction. The reaction mixture was precipitated in acetoneand the resultant solid product was filtered. The product was subjectedto Soxhlet extraction with isopropanol for 72 hours and re-precipitatedfrom water into acetone. PVOH-g-Gly polymer was obtained as a whitesolid that was then dried in vacuum oven at 40° C. for 16 hours.Subscripts a and b correspond to the weight percentages of respectiverepeating units in the polymer.

The process described in Example 1 was repeated by varying the moleratios of one or more reactants PVOH and/or glycidol. Multiple samplesof PVOH-g-Gly polymers having different physicochemical properties wereobtained and tested for various personal care applications, particularlyin hair care. The hair care application data of some of these polymersis provided below.

Hair Care Application Tests and Results

Solution Preparation

An amount of 0.5 g of PVOH-g-Gly polymer and 9.5 g of deionized waterwere added to a 20 ml scintillation vial to make 5 weight % polymericsolutions. It was found that PVOH-g-Gly polymer was easy to dissolve byvortexing at room temperature. Additionally, no heat was required forsolution formation. The commercial unmodified PVOH (Selvol™ PVOH 350,Sekisui Specialty Chemicals) required around 1 hour of mixing at 85° C.with an overhead mixer to solubilize the polymer. The polymer solutionsso formed were tested for hair care applications as described below.

Hair Characteristics Test

Hair Tresses (6.5 inches, 3.5 g Dark Brown virgin) were treated with 0.5g of polymer solution, rolled, dried, and evaluated for typical stylingcharacteristics in a temperature and humidity controlled environment.Panelists (n=2) carefully released each tress from its roller so as tokeep curl as undisturbed as possible, and made subjective comparisonsusing a numerical system of scoring. The study included testing polymersolutions for shine or luster, stiffness, crunch, curl snap, smooth combthrough, lack of residue on comb, lack of residue on hair,manageability, and lack of static. FIG. 1 demonstrates the haircharacteristics test results of 5 weight % PVOH polymeric solution(control) in comparison with 5 weight % solution of PVOH-g-Gly polymer.PVOH-g-Gly polymers demonstrated outstanding hair stiffness, stiffnessdurability, and tack profile.

High Humidity Hair Curl Retention Test

Polymer Solution Composition

An amount of 0.35 g of 5 weight % polymer solution of PVOH andPVOH-g-Gly polymers was applied on to 6.5 inch 2 g Dark Brown virginhair tresses which were then set on rollers. After drying andequilibration at low humidity, tresses were removed and hung upright.The length of tresses was then quantified at 80° F. and 90% RH as afunction of time. Styling products are sensitive to initial “droop” ofcurl, so measurements of length were noted at 15, 30, 45, 60 and 90minutes before continuing with the 120, 180 and 240-minute readings.Testing was performed on four tresses to ensure statistical rigor. ThePVOH-g-Gly polymers were much easier to process and incorporate intosolution. The high humidity curl retention property of PVOH-g-Glypolymer solution was outstanding.

Polymer Gel Composition

A gel composition comprising 2.5 weight % of PVOH-g-Gly polymer wasprepared and its performance compared with gel compositions comprising2.5 weight % of PVOH (control) polymers. The ingredients of gelcompositions are shown in Table 1.

TABLE 1 Gel composition ingredients PVOH PVOH-g-Gly Gel In- Gel In-Trade Name gredients gredients Phase Ingredient (manufacturer) % w/w %w/w A Water — 36.20 36.20 Carbomer Carbomer ™ 980 33.30 33.30 (1.5 wt %)(Ashland Inc.) B Water — 5.00 5.00 Aminomethyl AMP Ultra ™ PC 0.50 0.50propanol 2000 (Dow) C 10% PVOH Selvol ™ PVOH 25.00 0.00 polymer solution350 (Sekisui Specialty Chemicals) 10% PVOH-g-Gly — 0.00 25.00 polymersolution Total 100.00 100.00 Property pH 7.1 7.45 Property Viscosity65,600 62,600 (Brookfield RVT Spindle #7, 20 RPM, 1 min)

The polymer comprising gels were tested for hair curl retention at 80°F. and 90% RH on hair tresses by using a method identical to polymersolution testing described above. The high humidity curl retentionproperty of PVOH-g-Gly polymer gels was outstanding. FIG. 2 demonstratesthe test results. The PVOH-g-Gly polymer comprising gels were easy toapply and distribute through the hair, very little foaming was observed,detangling or wet combing was very easy, and there was no tack.

What is claimed is:
 1. A hair care composition comprising: (i) a polymerhaving the structure of:

wherein “a” is a value ranging from about 0.1 to 100 percent by weightof said polymer; and “b” is from 0 to about 99.9 percent by weight ofsaid polymer, with the proviso that sum of said “a” and “b” for saidpolymer equals 100 weight percent; and (ii) at least one hair careadditive selected from the group consisting of hair care agents, hairstyling agents, hair fixative agents, film formers, structurants,gelling agents, surfactants, thickeners, preservatives, viscositymodifiers, electrolytes, pH adjusting agents, perfumes, dyes,organosilicon compounds, anti-dandruff agents, anti-foaming agents,anti-frizz agents, penetrants, vitamins, conditioning agents, chelatingagents, antimicrobial agents, preservatives, UV absorbers, sunscreens,anti-oxidants, anti-radical protecting agents, natural extractspropellants, carriers, diluents, solvents, pharmaceutical actives,lubricants, combing aids, plasticizers, solubilizers, neutralizingagents, vapor pressure suppressants, bleaching agents, hydrating agents,moisturizers, pharmaceutically or cosmetically acceptable adjuvantsand/or additives, protectants, and combinations thereof.
 2. The haircare composition according to claim 1 wherein said hair care compositionis a hair styling composition.
 3. The hair care composition according toclaim 2 wherein said hair styling composition provides hairstyleretention at a relative humidity exceeding about 40 percent.
 4. The haircare composition according to claim 2 wherein said hair stylingcomposition is a gel, an aerosol, a pump spray, a sprig, a lotion, acream, or a mousse.
 5. The hair care composition according to claim 4wherein said hair styling composition is a hair styling gel.
 6. The haircare composition according to claim 1 wherein said polymer modifies therheology of said composition.